JP6414937B2 - Method for producing hydrogenated natural rubber latex - Google Patents
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- JP6414937B2 JP6414937B2 JP2016248763A JP2016248763A JP6414937B2 JP 6414937 B2 JP6414937 B2 JP 6414937B2 JP 2016248763 A JP2016248763 A JP 2016248763A JP 2016248763 A JP2016248763 A JP 2016248763A JP 6414937 B2 JP6414937 B2 JP 6414937B2
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- 229920006173 natural rubber latex Polymers 0.000 title claims description 109
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims description 106
- 239000003054 catalyst Substances 0.000 claims description 85
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 229920001971 elastomer Polymers 0.000 claims description 25
- 239000005060 rubber Substances 0.000 claims description 25
- 229910052707 ruthenium Inorganic materials 0.000 claims description 14
- -1 ruthenium halide compound Chemical class 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 230000003544 deproteinization Effects 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000009472 formulation Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 description 53
- 230000000052 comparative effect Effects 0.000 description 37
- 229920000126 latex Polymers 0.000 description 28
- 239000004816 latex Substances 0.000 description 28
- 244000043261 Hevea brasiliensis Species 0.000 description 22
- 229920003052 natural elastomer Polymers 0.000 description 22
- 229920001194 natural rubber Polymers 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 229910019891 RuCl3 Inorganic materials 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 150000003304 ruthenium compounds Chemical class 0.000 description 7
- 229920000459 Nitrile rubber Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000003623 transition metal compounds Chemical class 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001059 synthetic polymer Polymers 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 2
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012668 chain scission Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011984 grubbs catalyst Substances 0.000 description 2
- UAORAKLVHWMDLY-UHFFFAOYSA-N hydrazine hydrogen peroxide Chemical compound NN.OO UAORAKLVHWMDLY-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- JMXMXKRNIYCNRV-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol Chemical compound OCP(CO)CO JMXMXKRNIYCNRV-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920006168 hydrated nitrile rubber Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000011326 mechanical measurement Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004441 surface measurement Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 229920006174 synthetic rubber latex Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は水素化天然ゴムラテックスに関するものであり、より詳細には、水素化触媒に水溶性ルテニウム化合物を選択することにより、反応に用いる天然ゴムラテックスの濃度が高い状態でも凝集することなく、安定的に水素化反応が進行することを可能とする、高濃度の水素化天然ゴムラテックスの製造方法に関するものである。 The present invention relates to a hydrogenated natural rubber latex, and more specifically, by selecting a water-soluble ruthenium compound as a hydrogenation catalyst, the natural rubber latex used in the reaction is stable without agglomeration even in a high concentration state. In particular, the present invention relates to a method for producing a hydrogenated natural rubber latex having a high concentration that allows a hydrogenation reaction to proceed.
主鎖に二重結合を含むポリマーの改質は、水素化触媒の存在下で水素ガスを導入し、炭素−炭素二重結合を水素化する方法が一般的に用いられている。
一般に、ポリマーの主鎖に二重結合を含むものは、酸素やオゾンの存在下、酸化反応等により主鎖切断を引き起こし、耐久性が低下し、脆くなり、それらは致命的な欠点であった。その為、例えば、スチレン−イソプレン（ブタジエン）ブロック共重合ゴム（ＳＩＳ，ＳＢＳ）（特許文献１）、環状アモルファスポリオレフィン類（特許文献２）、ブタジエン−アクリロニトリル共重合ゴム（ＮＢＲ）（特許文献３）では、水素化反応により、炭素−炭素二重結合を水素化し、耐久性の向上を図っている。
For reforming a polymer containing a double bond in the main chain, a method of hydrogenating a carbon-carbon double bond by introducing hydrogen gas in the presence of a hydrogenation catalyst is generally used.
In general, polymers containing double bonds in the main chain of the polymer cause main chain scission by oxidation reaction in the presence of oxygen or ozone, resulting in decreased durability and brittleness, which are fatal defects. . Therefore, for example, styrene-isoprene (butadiene) block copolymer rubber (SIS, SBS) (Patent Document 1), cyclic amorphous polyolefins (Patent Document 2), butadiene-acrylonitrile copolymer rubber (NBR) (Patent Document 3). In this case, the carbon-carbon double bond is hydrogenated by a hydrogenation reaction to improve durability.
その中でも特に、特許文献１及び２では、触媒を用いながら水素化反応を効率良く行う為、ジエン系ポリマーを多量の有機溶媒中に溶解させる均一下で水素化反応が行われ、その為、反応速度が速く、触媒の使用量が抑えられ、更には触媒除去が簡便であり、この方法は一般的に多く採用されている。
特許文献３のＮＢＲの場合、有機溶媒を用いずに、ラテックス状態である不均一系で水素化反応が行われている。ＮＢＲはブタジエンユニットを含むジエン系合成ポリマーである為、反応性が高く、また、ラテックスの粒径が小さい合成ポリマーであり、天然ゴムに含まれる蛋白質のような触媒毒になる物質が含有されていないことから、反応阻害が少なく、触媒の使用量を抑えられ、工業的な製造方法が確立され、ＨＮＢＲとして一般に流通されている。
In particular, in Patent Documents 1 and 2, in order to efficiently perform a hydrogenation reaction using a catalyst, a hydrogenation reaction is performed under a uniform condition in which a diene polymer is dissolved in a large amount of an organic solvent. The speed is high, the amount of the catalyst used is suppressed, and the catalyst removal is simple, and this method is generally employed in many cases.
In the case of NBR of Patent Document 3, the hydrogenation reaction is performed in a heterogeneous system in a latex state without using an organic solvent. Since NBR is a diene-based synthetic polymer containing butadiene units, NBR is a synthetic polymer that has high reactivity and a small particle size of latex, and contains substances that become catalyst poisons such as proteins contained in natural rubber. Since there is no reaction inhibition, there is little reaction inhibition, the usage-amount of a catalyst can be restrained, an industrial manufacturing method is established, and it distribute | circulates generally as HNBR.
一方、天然ゴムを用いた水素化触媒による水素化反応は、固形の天然ゴムを有機溶媒中に溶解させる均一系で行われている。（非特許文献１〜３）
この場合、天然ゴムの濃度として、全配合物１００重量％に対して２〜５重量％と非常に低い濃度で反応が行われ、生産効率が悪い上、多量の有機溶媒を使用することから作業環境に悪く、工業的量産化には更なる改良が必要であった。
On the other hand, the hydrogenation reaction by the hydrogenation catalyst using natural rubber is performed in a homogeneous system in which solid natural rubber is dissolved in an organic solvent. (Non-patent documents 1 to 3)
In this case, the reaction is performed at a very low concentration of 2 to 5% by weight with respect to 100% by weight of the total blend, and the production efficiency is poor and a large amount of organic solvent is used. It was bad for the environment, and further improvements were necessary for industrial mass production.
従って、高い生産効率で且つ有機溶剤を用いずに水素化反応を行う必要があり、その為には、天然ゴムラテックスを直接水素化する方法が好ましく、近年では、天然ゴムラテックスを用いた水素化反応を行う方法が各種提案されている。
天然ゴムラテックスの水素化反応として、（Ａ）遷移金属化合物触媒を用いる方法と、（Ｂ）ヒドラジン−過酸化水素によるジイミド中間体を形成させて水素化する方法がある。（非特許文献４、５）
（Ｂ）ヒドラジン−過酸化水素による方法では、架橋や主鎖切断などの副反応が起こりやすいという欠点があり、また、近年ではヒドラジンの毒性が問題となり、天然ゴムラテックスの水素化方法としては（Ａ）の遷移金属化合物触媒を用いる方法が多く採用されている。
Therefore, it is necessary to carry out a hydrogenation reaction with high production efficiency and without using an organic solvent. For this purpose, a method of directly hydrogenating natural rubber latex is preferred. Recently, hydrogenation using natural rubber latex is preferred. Various methods for carrying out the reaction have been proposed.
As a hydrogenation reaction of natural rubber latex, there are (A) a method using a transition metal compound catalyst and (B) a method of hydrogenating by forming a diimide intermediate with hydrazine-hydrogen peroxide. (Non-Patent Documents 4 and 5)
(B) The hydrazine-hydrogen peroxide method has the disadvantage that side reactions such as cross-linking and main chain scission are likely to occur, and in recent years, the toxicity of hydrazine has become a problem. Many methods using the transition metal compound catalyst of A) are employed.
（Ａ）遷移金属化合物触媒を用いた方法では、パラジウム、ロジウム、ルテニウムをベースとする化合物を用いた水素化反応が提案されている。（非特許文献６）
天然ゴムラテックスの水素化は、ジエン系合成ラテックスを用いた場合と異なり、天然ゴムラテックス中に含まれる蛋白質などの不純物が水素化反応を阻害することや、合成ポリマーに比べて粒径が大きいことなどの理由で、反応速度が遅く、天然ゴムラテックスの水素化は困難であった。その為、脱蛋白化処理された脱蛋白化天然ゴムラテックスを用いた水素化反応が行われている。
(A) In the method using a transition metal compound catalyst, a hydrogenation reaction using a compound based on palladium, rhodium or ruthenium has been proposed. (Non-patent document 6)
Unlike when diene synthetic latex is used, hydrogenation of natural rubber latex is that impurities such as proteins contained in natural rubber latex inhibit the hydrogenation reaction and that the particle size is larger than that of synthetic polymer. For these reasons, the reaction rate was slow, and it was difficult to hydrogenate natural rubber latex. Therefore, a hydrogenation reaction using a deproteinized natural rubber latex that has been subjected to a deproteinization treatment is performed.
遷移金属化合物触媒を用いた例では、パラジウム化合物を用いた水素化天然ゴムラテックスの製造方法が提案されている。（特許文献４、５）
特許文献４及び５は、塩化パラジウムを主体とする触媒を用いた反応が行われているが、本発明者は特許文献４及び５を追試した結果、本特許の比較例１に示す通り、反応条件によっては反応効率が悪く、その為十分な再現性が得られず、また、脱蛋白化天然ゴムラテックスでしか水素化反応が進行しないといった、数々の問題点があった。
In an example using a transition metal compound catalyst, a method for producing a hydrogenated natural rubber latex using a palladium compound has been proposed. (Patent Documents 4 and 5)
In Patent Documents 4 and 5, a reaction using a catalyst mainly composed of palladium chloride is carried out. As a result of further examination of Patent Documents 4 and 5, the present inventor reacted as shown in Comparative Example 1 of this patent. Depending on the conditions, the reaction efficiency is poor, so that sufficient reproducibility cannot be obtained, and the hydrogenation reaction proceeds only with deproteinized natural rubber latex.
一方、触媒にルテニウム化合物を用いた例では、非水溶性の触媒として、メタセシス反応に用いられるＧｒｕｂｂｓ触媒や第二世代のＧｒｕｂｂｓ触媒を用いた天然ゴムラテックスの水素化反応が提案されている。（非特許文献７、特許文献６）
この場合、Ｇｒｕｂｂｓ触媒のような高価な触媒を用いていることや、天然ゴム濃度が非常に低い状態（全配合物１００重量％に対して、固形分濃度が１〜２重量％）で検討されていることから、生産コストが高い上、生産効率が悪いという問題点があり、更に、特許文献４及び５と同様に、脱蛋白化天然ゴムラテックスを用いたものでしか例示されていなかった。
On the other hand, in an example in which a ruthenium compound is used as a catalyst, a hydrogenation reaction of natural rubber latex using a Grubbs catalyst used in a metathesis reaction or a second generation Grubbs catalyst as a water-insoluble catalyst has been proposed. (Non-patent document 7, Patent document 6)
In this case, it is considered that an expensive catalyst such as a Grubbs catalyst is used, or that the natural rubber concentration is very low (the solid concentration is 1 to 2% by weight with respect to 100% by weight of the total formulation). Therefore, there is a problem that the production cost is high and the production efficiency is low. Further, as in Patent Documents 4 and 5, only those using a deproteinized natural rubber latex are exemplified.
更に、触媒に水溶性のルテニウム化合物を用いた例では、合成ゴムラテックスの水素化反応が行われ、ＮＢＲを用いた例（特許文献７、８）、ブタジエンゴムを用いた例（特許文献９）など様々な提案がされているが、これらの場合、天然ゴムラテックスを用いた検討は行われていなかった。 Furthermore, in an example using a water-soluble ruthenium compound as a catalyst, a hydrogenation reaction of a synthetic rubber latex is performed, an example using NBR (Patent Documents 7 and 8), an example using butadiene rubber (Patent Document 9). Various proposals have been made, but in these cases, studies using natural rubber latex have not been conducted.
本発明の目的は、水素化天然ゴムラテックスの製造において、濃度の高い天然ゴムラテックスを用いて、安定的に高濃度の水素化天然ゴムラテックスを製造する方法であり、従来の製造方法に比べ、生産効率が向上し、簡易的且つ安価に製造する方法を提供することにある。 An object of the present invention is a method for stably producing a high concentration hydrogenated natural rubber latex using a natural rubber latex having a high concentration in the production of a hydrogenated natural rubber latex, compared with a conventional production method, An object of the present invention is to provide a simple and inexpensive manufacturing method with improved production efficiency.
上述の課題を解決するために、本発明者は鋭意検討した結果、以下の構成により解決することを見出した。
即ち、本発明は、
１．脱蛋白化処理を施さない天然ゴムラテックスを原材料に、水素化触媒の存在下、有機溶媒を用いずに、水素と反応させて得られる水素化天然ゴムラテックスであって、
前記天然ゴムラテックス中のゴム分は、水を含む全配合物の１００重量％に対して１０重量％以上含有し、
前記水素化触媒は、水溶性ハロゲン化ルテニウム化合物であり、
連続的又は間欠的に触媒を添加することを特徴とする水素化天然ゴムラテックスの製造方法。
２．前記水素化天然ゴムラテックス中の水素添加物の水素添加率が６５％以下であることを特徴とする請求項１に記載の水素化天然ゴムラテックスの製造方法。
３．前記水素化反応の反応温度が６０℃〜１５０℃であることを特徴とする請求項１〜２のいずれかに記載の水素化天然ゴムラテックスの製造方法。
In order to solve the above-mentioned problems, the present inventor has intensively studied, and as a result, has found that the following configuration can solve the problem.
That is, the present invention
1. A hydrogenated natural rubber latex obtained by reacting natural rubber latex not subjected to deproteinization treatment with hydrogen without using an organic solvent in the presence of a hydrogenation catalyst,
The rubber content in the natural rubber latex is 10% by weight or more with respect to 100% by weight of the total formulation including water,
The hydrogenation catalyst is a water-soluble ruthenium halide compound,
A method for producing a hydrogenated natural rubber latex, wherein the catalyst is added continuously or intermittently.
2 . The method for producing a hydrogenated natural rubber latex according to claim 1, wherein a hydrogenation rate of a hydrogenated product in the hydrogenated natural rubber latex is 65% or less.
3 . The method for producing a hydrogenated natural rubber latex according to any one of claims 1 to 2 , wherein a reaction temperature of the hydrogenation reaction is 60 ° C to 150 ° C.
本発明によれば、天然ゴムラテックスの濃度が高い状態で水素化反応させることにより、高濃度の水素化天然ゴムラテックスが得られ、効率的且つ安価な水素化天然ゴムラテックスの製造方法を提供することを可能とする。 According to the present invention, a hydrogenated natural rubber latex having a high concentration can be obtained by performing a hydrogenation reaction in a state where the concentration of the natural rubber latex is high, and an efficient and inexpensive method for producing a hydrogenated natural rubber latex is provided. Make it possible.
以下に本発明の実施形態を詳細に説明する。
本発明の水素化天然ゴムラテックスは、天然ゴムラテックスを原材料に、水素化触媒の存在下、水素と反応させて得られるものである。
原材料の天然ゴムラテックスとしては、（１）脱蛋白処理を施さない天然ゴムラテックス、（２）脱蛋白処理を施した脱蛋白化天然ゴムラテックスから選択されるが、
（１）脱蛋白処理を施さない天然ゴムラテックスとしては、フィールドラテックス、アンモニアを含有した高アンモニアタイプのＨＡラテックス、低アンモニアタイプのＬＡラテックス、濃縮前のフィールドラテックスにアンモニア処理等を施し、二回以上の遠心分離により非ゴム分を１％未満に抑えた高精製ラテックス、等を用いることができる。
（２）脱蛋白天然ゴムラテックスとしては、酵素を添加して蛋白質を分解し、界面活性剤で処理した後、精製する酵素処理による脱蛋白化タイプのものや、尿素処理により蛋白質を除去し精製した脱蛋白化タイプのものがある。
これらは単独でも、あるいは複数を組み合わせても使用してもよい。
その中でも、触媒使用量の最適化から好ましくは、酵素処理天然ゴムラテックスや尿素処理天然ゴムラテックスを用いて遠心分離処理を行った脱蛋白化天然ゴムラテックスであり、コスト面や性能面から最も好ましくは、遠心分離を二回以上行い非ゴム分を１％未満に抑えた高精製天然ゴムラテックスである。
Hereinafter, embodiments of the present invention will be described in detail.
The hydrogenated natural rubber latex of the present invention is obtained by reacting natural rubber latex with hydrogen in the presence of a hydrogenation catalyst.
The raw natural rubber latex is selected from (1) natural rubber latex not subjected to deproteinization treatment, and (2) deproteinized natural rubber latex subjected to deproteinization treatment.
(1) Natural rubber latex not subjected to deproteinization treatment includes field latex, high ammonia type HA latex containing ammonia, low ammonia type LA latex, field latex before concentration, ammonia treatment, etc. twice. A highly purified latex having a non-rubber content reduced to less than 1% by the above centrifugation can be used.
(2) As deproteinized natural rubber latex, an enzyme is added to decompose the protein, and after treatment with a surfactant, the protein is deproteinized by enzyme treatment to be purified, or purified by removing the protein by urea treatment. There is a deproteinized type.
These may be used alone or in combination.
Among them, a deproteinized natural rubber latex obtained by performing a centrifugal separation process using an enzyme-treated natural rubber latex or a urea-treated natural rubber latex is most preferable from the viewpoint of cost and performance. Is a highly purified natural rubber latex that is centrifuged twice or more to keep the non-rubber content below 1%.
上記、天然ゴムラテックスのゴム分濃度としては、水を含む全配合物の１００重量％に対して１０重量％以上含有することが好ましい。生産効率を高める為に、更に好ましくは２０重量％以上であり、より好ましくは２５重量％以上であり、最も好ましくは３０重量％以上含有することである。
即ち、ラテックスが凝集しない限りにおいて、水素化天然ゴムラテックスの生産効率を向上させる為には、ゴム分濃度が高いことが望ましい。
The rubber content concentration of the natural rubber latex is preferably 10% by weight or more with respect to 100% by weight of the total formulation including water. In order to increase production efficiency, it is more preferably 20% by weight or more, more preferably 25% by weight or more, and most preferably 30% by weight or more.
That is, as long as the latex does not aggregate, it is desirable that the rubber concentration is high in order to improve the production efficiency of the hydrogenated natural rubber latex.
水素化触媒としては、ルテニウム化合物が好ましく、非水溶性又は水溶性の触媒から選択されるが、非特許文献７や特許文献６で用いられている第二世代のＧｒｕｂｂｓ触媒のような非水溶性の触媒を用いた場合、有機溶媒等を用いてラテックス中に可溶化させる必要があり、その為、有機溶媒を用いずに行うには、水溶性触媒であることが好ましく、即ち、水溶性のルテニウム化合物であることが好ましい。
水溶性のルテニウム化合物としては、ハロゲン化ルテニウム、硫酸ルテニウム、硝酸ルテニウム、酢酸ルテニウム、ルテニウムニトロシルハライド、などの無機又は有機酸塩、トリス（ヒドロキシメチル）ホスフィンを配位子とするルテニウム錯体、１，２−ビス（ジヒドロキシメチルホスフィノ）エタンを配位子とするルテニウム錯体などを挙げることができる。
これらの中で、ハロゲン化ルテニウムが好ましい。
ハロゲン化ルテニウムとしては、塩化ルテニウム（ＲｕＣｌ３）、臭化ルテニウム（ＲｕＢｒ３）、ヨウ化ルテニウム（ＲｕＩ３）などがある。 この中で、価格面や反応性の点などから、塩化ルテニウム（ＲｕＣｌ３）が最も好ましい。
これらは単独でも、あるいは複数を組み合わせても使用してもよい。
The hydrogenation catalyst is preferably a ruthenium compound and is selected from water-insoluble or water-soluble catalysts, but water-insoluble such as the second generation Grubbs catalyst used in Non-Patent Document 7 and Patent Document 6. When the above catalyst is used, it is necessary to solubilize it in the latex using an organic solvent or the like. Therefore, in order to carry out without using an organic solvent, a water-soluble catalyst is preferable. A ruthenium compound is preferred.
Examples of the water-soluble ruthenium compound include ruthenium halide, ruthenium sulfate, ruthenium nitrate, ruthenium acetate, ruthenium nitrosyl halide, and the like, ruthenium complexes having tris (hydroxymethyl) phosphine as a ligand, 1, Examples thereof include a ruthenium complex having 2-bis (dihydroxymethylphosphino) ethane as a ligand.
Of these, ruthenium halide is preferred.
Examples of the ruthenium halide include ruthenium chloride (RuCl 3 ), ruthenium bromide (RuBr 3 ), and ruthenium iodide (RuI 3 ). Among these, ruthenium chloride (RuCl 3 ) is most preferable from the viewpoint of price and reactivity.
These may be used alone or in combination.
従来、水素化触媒として用いられていたハロゲン化パラジウムの場合、非水溶性の為、王水や塩酸などの強酸で溶解させる方法が用いられていたが、ラテックスの凝集を抑える為に、ラテックスの濃度を低濃度にする必要があった。また、本発明者らは特許文献４及び５を追試したところ、脱蛋白化処理を施さない天然ゴムラテックスでは反応がうまく進行しない結果となった。
一方、本発明の水素化触媒であるハロゲン化ルテニウムは、水溶性であり、溶解度が高く、強酸などの処理を必要としないことから、濃度の高い天然ゴムラテックスでも凝集せず、安定的に水素化反応するという特徴があり、また、ハロゲン化ルテニウムを用いて、後述する製造方法により水素化反応を行うことにより、脱蛋白処理を施さない天然ゴムラテックスでも水素化反応が進行することが可能である。
Conventionally, in the case of palladium halide used as a hydrogenation catalyst, a method of dissolving with a strong acid such as aqua regia or hydrochloric acid has been used because of water insolubility. The concentration needed to be low. In addition, the inventors of the present invention made additional efforts to Patent Documents 4 and 5, and as a result, the reaction did not proceed well with natural rubber latex not subjected to deproteinization treatment.
On the other hand, the ruthenium halide, which is the hydrogenation catalyst of the present invention, is water-soluble, has high solubility, and does not require treatment with a strong acid or the like. The hydrogenation reaction can proceed even in natural rubber latex that is not subjected to deproteinization treatment by using a ruthenium halide and performing a hydrogenation reaction by a production method described later. is there.
水素化反応において、触媒を連続的又は間欠的に数回に分けて添加する製造方法により、触媒使用量を最小限に留め、効率良く水素化反応が進行することを見出した。
また、高濃度の天然ゴムラテックスを用いた場合においても、この方法によれば、凝集することなく安定的に水素化天然ゴムラテックスを得られることができる。
特に天然ゴムラテックスのような不純物の多いポリマーへの水素化反応の場合、蛋白質などの触媒毒となるような物質が含有されていることから、反応阻害要因となり、触媒活性が低下し、水素化効率が悪くなる傾向がある為、水素化天然ゴムラテックスの反応には脱蛋白化処理を施した脱蛋白天然ゴムラテックスを用いた方が効率良く反応するという傾向がある。
本発明によれば、水溶性のハロゲン化ルテニウムを用いた水素化触媒を連続的又は間欠的に添加する製造方法により、脱蛋白化処理を施さない天然ゴムラテックスでも安定的に水素化反応が進行し、少ない触媒量で高濃度の水素化天然ゴムラテックスを得ることを可能とする。
It has been found that in the hydrogenation reaction, the amount of catalyst used is kept to a minimum and the hydrogenation reaction proceeds efficiently by a production method in which the catalyst is added continuously or intermittently in several portions.
Further, even when a high concentration natural rubber latex is used, according to this method, a hydrogenated natural rubber latex can be stably obtained without agglomeration.
Especially in the case of hydrogenation reaction to a polymer with many impurities such as natural rubber latex, it contains substances that can be catalyst poisons such as proteins, which may hinder the reaction and reduce the catalytic activity, resulting in hydrogenation. Since the efficiency tends to deteriorate, the reaction of the hydrogenated natural rubber latex tends to react more efficiently when the deproteinized natural rubber latex subjected to the deproteinization treatment is used.
According to the present invention, a hydrogenation catalyst using a water-soluble ruthenium halide is continuously or intermittently added, so that a hydrogenation reaction proceeds stably even in a natural rubber latex not subjected to deproteinization treatment. Thus, it is possible to obtain a high concentration hydrogenated natural rubber latex with a small amount of catalyst.
次に、本発明の水素化天然ゴムラテックスを製造する方法として、（１）水素化触媒の添加工程と（２）水素化反応工程について説明する。 Next, as a method for producing the hydrogenated natural rubber latex of the present invention, (1) a hydrogenation catalyst addition step and (2) a hydrogenation reaction step will be described.
（１）水素化触媒の添加工程において、
触媒は、窒素などで脱酸素化されたイオン交換水や蒸留水で希釈しておくことが好ましい。特に、連続的又は間欠的に添加する場合は、系内に酸素などが入り込まないように、窒素などの不活性ガス下で行うことが好ましい。触媒は、水溶性のルテニウムを単独でも、あるいは他の水素化触媒と複数を組み合わせても使用してもよい。ハロゲン化ルテニウムを用いる場合は、そのままの状態で使用してもよいし、ハロゲンの一部を他の配位子と置換させて使用してもよい。
(1) In the hydrogenation catalyst addition step,
The catalyst is preferably diluted with ion-exchanged water or distilled water deoxygenated with nitrogen or the like. In particular, when adding continuously or intermittently, it is preferably carried out under an inert gas such as nitrogen so that oxygen or the like does not enter the system. As the catalyst, water-soluble ruthenium may be used alone or in combination with other hydrogenation catalysts. When ruthenium halide is used, it may be used as it is, or a part of the halogen may be substituted with another ligand.
本発明で用いるハロゲン化ルテニウムでは初期活性が高い為、反応時間を短縮させる効果がある。
触媒使用量としては、天然ゴムラテックス中のゴム分に対して、０．０１〜５．０重量％のＲｕ量が好ましい。
特に、０．０２〜３．０重量％のＲｕ量が好ましく、より好ましくは０．０５〜２．０重量％のＲｕ量が好ましく、更に、０．１〜１．５重量％のＲｕ量が好ましく、最も好ましくは、０．２〜１．０重量％である。
０．０１重量％未満であると水素化反応が十分に進行しない場合があり、一方、５重量％を超えると、高コストになり好ましくない。
Since ruthenium halide used in the present invention has high initial activity, it has an effect of shortening the reaction time.
The amount of the catalyst used is preferably 0.01 to 5.0% by weight of Ru with respect to the rubber content in the natural rubber latex.
In particular, a Ru amount of 0.02 to 3.0% by weight is preferable, a Ru amount of 0.05 to 2.0% by weight is more preferable, and a Ru amount of 0.1 to 1.5% by weight is further preferable. Preferably, it is 0.2 to 1.0% by weight.
If the amount is less than 0.01% by weight, the hydrogenation reaction may not proceed sufficiently. On the other hand, if it exceeds 5% by weight, the cost increases, which is not preferable.
触媒をラテックスに添加する方法としては、全量を一括で添加する方法又は連続的又は間欠的に添加する方法を用いることができるが、触媒の失活による活性の減衰を考慮すると、触媒を連続的に添加又は間欠的に数回に分けて添加する方法が最も好ましい。
触媒を連続的又は間歇的に添加する方法としては、ポンプを使用して連続的に添加する方法や、ある量を含有した容器から都度添加する方法、触媒を徐放性の容器などに入れて触媒を徐放していく方法などがあるが、それらの方法は、特に限定するものではない。
連続的又は間欠的に添加する場合の触媒添加量は、最初の添加量をやや多めに添加し、その後は少量を連続的又は間欠的に添加することが好ましい。
As a method of adding the catalyst to the latex, a method of adding the whole amount at once or a method of adding it continuously or intermittently can be used. However, considering the decay of activity due to catalyst deactivation, the catalyst is continuously added. The most preferable method is to add to or intermittently divide into several times.
As a method of continuously or intermittently adding the catalyst, a method of continuously adding using a pump, a method of adding each time from a container containing a certain amount, or putting a catalyst in a sustained-release container, etc. There are methods such as slow release of the catalyst, but these methods are not particularly limited.
In the case of continuous or intermittent addition, it is preferable that the catalyst addition amount is slightly larger than the initial addition amount, and thereafter a small amount is added continuously or intermittently.
また、ラテックスの凝集を抑えるために、触媒又は天然ゴムラテックス中に界面活性剤を添加しても良い。
界面活性剤としては、アニオン系界面活性剤、ノニオン系界面活性剤及びカチオン系界面活性剤、両性界面活性剤などから選択できるが、その中でもラテックスの安定性の点から、アニオン系界面活性剤が好ましい。
In order to suppress latex aggregation, a surfactant may be added to the catalyst or natural rubber latex.
The surfactant can be selected from anionic surfactants, nonionic surfactants and cationic surfactants, amphoteric surfactants, etc. Among them, anionic surfactants are preferred from the viewpoint of latex stability. preferable.
次に、
（２）水素化反応工程において、
天然ゴムラテックスを水素化触媒の存在下、水素ガスを用いて反応させ、水素化天然ゴムラテックスを得る。
水素化反応は、水素の存在下、バッチ式、セミバッチ式、連続式、いずれかの方法を採用してもよい。
尚、水素化反応における酸素の存在は、ポリマーへの水素化を阻害する要因となり、酸化反応のような副反応をもたらす為、脱酸素下、例えば脱酸素状態でのラテックス中で行うことが好ましい。
また、上述した通り、水素化触媒を希釈する際は脱酸素化した状態で行う必要があり、又は別の方法として、天然ゴムラテックスと水素化触媒である水溶性ルテニウム触媒の水溶液を室温下で混合した後、脱酸素化する方法を用いることができ、作業の短縮となり、好ましい方法である。
next,
(2) In the hydrogenation reaction step,
Natural rubber latex is reacted with hydrogen gas in the presence of a hydrogenation catalyst to obtain hydrogenated natural rubber latex.
For the hydrogenation reaction, any of batch, semi-batch and continuous methods may be employed in the presence of hydrogen.
It should be noted that the presence of oxygen in the hydrogenation reaction is a factor that inhibits hydrogenation of the polymer and causes side reactions such as an oxidation reaction. Therefore, it is preferably performed in deoxygenated latex, for example, in a deoxygenated latex. .
Further, as described above, when diluting the hydrogenation catalyst, it is necessary to carry out in a deoxygenated state, or as another method, an aqueous solution of a natural rubber latex and a water-soluble ruthenium catalyst that is a hydrogenation catalyst at room temperature. After mixing, a method of deoxygenation can be used, which shortens the operation and is a preferable method.
水素化反応の反応温度は、触媒特性や反応条件から、特に６０℃〜１５０℃の温度範囲で行うことが好ましい。
６０℃未満では、反応速度が遅い為に水素添加化率が低くなる恐れがあり、１５０℃を超える反応温度では、ラテックスの安定性が悪く、凝集する恐れがあり、更に天然ゴム自体の劣化が起こりやすくなることから、好ましくない。
特に、８０℃〜１３０℃の温度範囲が好ましい。
The reaction temperature of the hydrogenation reaction is preferably carried out in the temperature range of 60 ° C. to 150 ° C., particularly from the catalyst characteristics and reaction conditions.
If the temperature is lower than 60 ° C, the hydrogenation rate may be low due to the slow reaction rate. If the reaction temperature is higher than 150 ° C, the stability of the latex may be poor and agglomeration may occur, and the natural rubber itself may deteriorate. This is not preferable because it tends to occur.
In particular, a temperature range of 80 ° C to 130 ° C is preferable.
反応時における圧力としては、触媒の種類や添加量などで異なるが、水溶性ルテニウム化合物を用いる場合には、大気圧〜１０ＭＰａであることが好ましく、より好ましくは０．３〜３ＭＰａである。
水素ガスの添加方法としては、圧力を一定に保つため、連続的に添加する方法や、間欠的に添加する方法を用いてもよい。
水素化反応後は、ラテックス中の触媒を除去することが好ましく、触媒の除去方法は、既知の方法を採用することにより、回収することができる。
The pressure during the reaction varies depending on the type of catalyst and the amount added, but when a water-soluble ruthenium compound is used, it is preferably atmospheric pressure to 10 MPa, more preferably 0.3 to 3 MPa.
As a method for adding hydrogen gas, a method of adding continuously or a method of adding intermittently may be used in order to keep the pressure constant.
After the hydrogenation reaction, the catalyst in the latex is preferably removed, and the catalyst can be recovered by adopting a known method.
得られた水素化天然ゴムラテックスの水素添加率は、一般に、水素添加率の上昇と共に耐久性が向上する為、好ましいとされるが、優れた力学特性を要求される用途において、特に天然ゴムの場合は、水素添加率が高すぎる状態であると好ましくない場合がある。
即ち、延伸結晶化や通常時の結晶・非結晶の問題があり、水素添加率が２／３を超える状態、即ち、６７％以上の水素添加率になると、結晶性が発現し始め、非特許文献５に記載されている通り、水素添加率が高い状態であると、天然ゴムの特徴である延伸結晶化が起こり難くなる傾向にあるとされている。
従って、力学特性が要求される用途においては、水素添加率は最大でも６５％以下が好ましく、より好ましくは５０％以下である。
一方、水素添加率が非常に状態である場合、例えば１０％以下では、耐久性の向上が得られない場合があり好ましくない。水素添加率は、力学特性が要求される用途・分野での使用においては、水素添加率は２０〜５０％が最も好ましい。
The hydrogenation rate of the obtained hydrogenated natural rubber latex is generally preferred because the durability improves as the hydrogenation rate increases. However, in applications that require excellent mechanical properties, it is particularly preferable for natural rubber. In some cases, it is not preferable that the hydrogenation rate is too high.
That is, there is a problem of stretched crystallization or normal / crystalline, and when the hydrogenation rate exceeds 2/3, that is, when the hydrogenation rate is 67% or more, crystallinity starts to appear, and non-patent As described in Document 5, when the hydrogenation rate is high, stretch crystallization, which is a characteristic of natural rubber, tends to hardly occur.
Therefore, in applications where mechanical properties are required, the hydrogenation rate is preferably 65% or less, more preferably 50% or less.
On the other hand, when the hydrogenation rate is very high, for example, if it is 10% or less, durability may not be improved, which is not preferable. The hydrogenation rate is most preferably 20 to 50% for use in applications and fields where mechanical properties are required.
また、本発明で得られた水素化天然ゴムラテックスは、原料として用いる天然ゴムラテックスと比較した場合、やや高い熱分解温度を示した。従って、それは、水素添加率の向上と共に、分解温度が上昇し、耐久性が向上することを示している。
更に、本実施例から分かる通り、得られた水素化天然ゴムラテックスは、伸長率が向上し、弾性率、破断点強度は低下する傾向にある。
このことから、恐らく、本発明法で製造された水素化天然ゴムは、ゴムとリン脂質間のエステル結合が（一部又は全て）切断されたものと推定される。
Moreover, the hydrogenated natural rubber latex obtained in the present invention showed a slightly higher thermal decomposition temperature when compared with the natural rubber latex used as a raw material. Therefore, it shows that the decomposition temperature increases and the durability improves with the improvement of the hydrogenation rate.
Furthermore, as can be seen from this example, the obtained hydrogenated natural rubber latex tends to have an improved elongation and a lower elastic modulus and strength at break.
From this, it is presumed that the hydrogenated natural rubber produced by the method of the present invention is one in which the ester bond between the rubber and the phospholipid is broken (partially or entirely).
本発明で得られた水素化天然ゴムラテックスは、必要に応じて加硫剤、架橋剤、無機充填剤などの補強材等を配合した組成物として調整し、更に水素添加率の制御を行うことにより、所望の性能が得られ、特に高い耐熱性や耐候性が求められる自動車用部材に適した用途であり、また、形状がラテックス状であることと、伸長率が向上するという特性から、浸漬成型加工を行う用途にも適している。
以下に実施例を挙げて本発明について具体的に説明するが、本発明は、これらの実施例に限定されるものではない。
The hydrogenated natural rubber latex obtained in the present invention is adjusted as a composition containing a reinforcing material such as a vulcanizing agent, a crosslinking agent, and an inorganic filler, if necessary, and further the hydrogenation rate is controlled. The desired performance is obtained, and it is an application suitable for automotive parts that require particularly high heat resistance and weather resistance. Also, from the characteristics that the shape is latex and the elongation rate is improved, Also suitable for molding applications.
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
本実施例及び比較例における評価方法を、以下に説明する。
（１）シートの作成：水素化品及び未水素化品のシート化ガラス板に原料天然ゴムラテックス及び実施例で得られた水素化天然ゴムラテックスを流し込み、水分を蒸発させてシートを作製した。シートの厚みは、０．３〜０．８ｍｍ程度とした。
（２）水素化率の測定：（株）島津製作所社製のフーリエ変換赤外分光光度計（ＦＴ−ＩＲ）を使用して、水素化率を求めた。未水素化品のＮＲシート、水素化品のＮＲシートをＦＴ−ＩＲでガラス面、及び空気面の両面をＡＴＲ法で測定し、８３３cm−１と１３７０ｃｍ−１の比較から、水素化率を求めた。（ガラス面と空気面では異なるので、平均値を採用して、水素化率とした。）
（３）力学特性の測定：力学特性の測定は、（株）島津製作所社製のオートグラフＡＧＳ−１ｋｇＮＧを使用した。厚さ；０．３〜０．８ｍｍ程度の水添物、未水添物、原料ＮＲのシートから４号ダンベルを切り出し、５００ｍｍ／ｍｉｎの速度で引張試験を行った。
（４）分解温度の測定：分解温度の評価は、ＳＩＩのＤＴＡ装置を使用し、窒素ガス流通下、室温から５００℃まで１０℃／ｍｉｎの速度で測定した。
The evaluation method in a present Example and a comparative example is demonstrated below.
(1) Preparation of sheet: The raw natural rubber latex and the hydrogenated natural rubber latex obtained in Examples were poured into hydrogenated and unhydrogenated sheeted glass plates, and water was evaporated to prepare a sheet. The thickness of the sheet was about 0.3 to 0.8 mm.
(2) Measurement of hydrogenation rate: The hydrogenation rate was determined using a Fourier transform infrared spectrophotometer (FT-IR) manufactured by Shimadzu Corporation. Measure NR sheet of unhydrogenated product, NR sheet of hydrogenated product by FT-IR on both glass surface and air surface by ATR method, and obtain hydrogenation rate from comparison of 833cm- 1 and 1370cm- 1. It was. (Since the glass surface and the air surface are different, the average value was adopted as the hydrogenation rate.)
(3) Measurement of mechanical properties: For the measurement of mechanical properties, Autograph AGS-1 kgNG manufactured by Shimadzu Corporation was used. Thickness: No. 4 dumbbell was cut out from a sheet of hydrogenated material, unhydrogenated material, raw material NR of about 0.3 to 0.8 mm, and a tensile test was performed at a speed of 500 mm / min.
(4) Measurement of decomposition temperature: The evaluation of the decomposition temperature was performed using a SII DTA apparatus at a rate of 10 ° C./min from room temperature to 500 ° C. under a nitrogen gas flow.
＜触媒調整＞
水素化触媒である市販の塩化ルテニウム等を、イオン交換水に適量添加し、触媒を作製・調製した。
例えば、塩化ルテニウムＲｕＣｌ３の水溶液（固形分濃度３．８重量％）を作成する場合、和光純薬工業（株）社製の塩化ルテニウム（ＩＩＩ）ｎ水和物を用いて、ＲｕＣｌ３・ｎＨ２Ｏを５．０ｇ秤量し、イオン交換水で希釈して、ＲｕＣｌ３水溶液１３１ｇを調製した。
尚、塩化ルテニウム（ＩＩＩ）ｎ水和物を用いた場合、Ｒｕ濃度は４３．１重量％として計算し、上記のＲｕＣｌ３水溶液中におけるＲｕ濃度としては、１．６４重量％である。
<Catalyst adjustment>
An appropriate amount of commercially available ruthenium chloride as a hydrogenation catalyst was added to ion-exchanged water to prepare and prepare a catalyst.
For example, when preparing an aqueous solution of ruthenium chloride RuCl 3 (solid content concentration: 3.8% by weight), RuCl 3 · nH is used by using ruthenium (III) chloride n hydrate manufactured by Wako Pure Chemical Industries, Ltd. 5.0 g of 2 O was weighed and diluted with ion-exchanged water to prepare 131 g of an aqueous RuCl 3 solution.
When ruthenium (III) chloride n hydrate is used, the Ru concentration is calculated as 43.1 wt%, and the Ru concentration in the RuCl 3 aqueous solution is 1.64 wt%.
＜原料の天然ゴム及び水素化天然ゴムの力学特性＞
表１に原材料として用いた天然ゴムラテックスの種類とそれらをシート化したシートの力学特性、等の性能を示す。
Table 1 shows the types of natural rubber latex used as a raw material and the performance such as the mechanical properties of the sheet made from the same.
（実施例１）
原料の天然ゴムラテックスとして（Ｂ）遠心分離処理を複数回施したハイアンモニアタイプの高精製天然ゴムラテックス（マレーシア産、ゴム分濃度６０．１重量％、非ゴム分０．７重量％）を用いて１５０ｇビーカーに投入し、次に、界面活性剤を３ｇ投入後、撹拌混合し、更にイオン交換水１８２ｇを加え撹拌混合し、オートクレーブ容器内のラテックスを窒素ガス置換してラテックス中の溶存酸素を除去した。
次に、（ｂ）３回に分けて添加する方法は、上記の手順により調製したＲｕＣｌ３触媒の水溶液２５ｇを、予め全量のうち１／２を原料の天然ゴムラテックスに混合し、オートクレーブ内を水素ガス置換し、水素ガスを１．２ＭＰａに加圧し、１００℃になるまで急昇温し、オートクレーブ内の圧力を１．２ＭＰａに維持し、１００℃で４時間水素化反応を行った。 次いで触媒量の１／４を配合し４時間水素化反応を行い、更に残りの触媒量１／４を配合して、合計１２時間水素化反応を行った。水素化の進行状況は、圧力の低下から判断し、圧力が１．０ＭＰａに低下すると水素を継ぎ足す方法で水素化を続行させた。
このときのゴム分濃度は、全配合物量１００重量％に対して、ゴム分濃度を２５重量％とした。
実施例１で得られた水素化天然ゴムラテックスは凝集せず安定なラテックス状態であった。
得られた水素化天然ゴムラテックス中における水素化天然ゴムの水素添加率は、２８％であった。
Example 1
(B) High-ammonia type highly purified natural rubber latex (produced in Malaysia, rubber concentration 60.1% by weight, non-rubber content 0.7% by weight) that has been subjected to centrifugal treatment multiple times. 150 g beaker, and then 3 g of surfactant is added and mixed with stirring. Further, 182 g of ion-exchanged water is added and stirred and mixed, and the latex in the autoclave container is replaced with nitrogen gas to dissolve dissolved oxygen in the latex. Removed.
Next, (b) the method of adding in three steps is to mix 25 g of an aqueous solution of RuCl3 catalyst prepared by the above procedure with 1/2 of the total amount of natural rubber latex as a raw material in advance, and the inside of the autoclave is hydrogenated. The gas was replaced, hydrogen gas was pressurized to 1.2 MPa, the temperature was rapidly increased to 100 ° C., the pressure in the autoclave was maintained at 1.2 MPa, and a hydrogenation reaction was performed at 100 ° C. for 4 hours. Next, 1/4 of the catalyst amount was blended and subjected to a hydrogenation reaction for 4 hours, and the remaining catalyst amount of 1/4 was blended to conduct a hydrogenation reaction for a total of 12 hours. The progress of hydrogenation was judged from the decrease in pressure. When the pressure decreased to 1.0 MPa, hydrogenation was continued by adding hydrogen.
At this time, the rubber concentration was 25% by weight with respect to 100% by weight of the total blend.
The hydrogenated natural rubber latex obtained in Example 1 did not aggregate and was in a stable latex state.
The hydrogenation rate of the hydrogenated natural rubber in the obtained hydrogenated natural rubber latex was 28%.
（実施例２）
触媒の添加方法を（ｂ´）５回に分けて添加する方法に変更し、反応時間を１２時間に変更した以外は実施例１と同様の方法で行った。
尚、（ｂ´）５回に分けて添加する方法は、予め触媒量の全量のうち１／３の量を原料の天然ゴムラテックスに混合し、水素化反応を２時間行った後、次いで２．５時間ごとに触媒量の１／６を添加し、それを４回繰り返し、合計１２時間水素化反応を行った。
得られた水素化天然ゴムラテックス中における水素化天然ゴムの水素添加率は、３５％であった。
(Example 2)
The catalyst was added in the same manner as in Example 1 except that the method for adding the catalyst was changed to (b ') a method in which the catalyst was added in 5 portions and the reaction time was changed to 12 hours.
In addition, (b ') the method of adding in 5 times is to mix 1/3 of the total amount of the catalyst in advance with the raw natural rubber latex and perform the hydrogenation reaction for 2 hours, then 2 1/6 of the catalyst amount was added every 5 hours, and this was repeated 4 times to carry out a hydrogenation reaction for a total of 12 hours.
The hydrogenation rate of the hydrogenated natural rubber in the obtained hydrogenated natural rubber latex was 35%.
（実施例３）
原料の天然ゴムラテックスに（Ｃ）脱蛋白処理を施さない天然ゴムラテックスであるハイアンモニアタイプの天然ゴムラテックス（マレーシア産、ゴム分濃度６０．２重量％、非ゴム分１．３重量％）に変更し、反応温度を１２０℃に変更した以外は、実施例２と同様の方法で行った。
得られた水素化天然ゴムラテックス中における水素化天然ゴムの水素添加率は、３５％であった。
(Example 3)
(C) High ammonia type natural rubber latex (made in Malaysia, rubber concentration 60.2 wt%, non-rubber content 1.3 wt%) which is a natural rubber latex that is not subjected to deproteinization treatment. The procedure was the same as in Example 2 except that the reaction temperature was changed to 120 ° C.
The hydrogenation rate of the hydrogenated natural rubber in the obtained hydrogenated natural rubber latex was 35%.
（比較例１〜２）
原料の天然ゴムラテックスとして（Ａ）脱蛋白質天然ゴムラテックスである住友精化（株
）社のセラテックス１１０１（ゴム分濃度６０重量％）を１２０ｇビーカーに投入し、次に、界面活性剤を３ｇ投入後、撹拌混合し、次に、（ａ）触媒添加方法は、予め全量を原料の天然ゴムラテックスに一括添加する方法を用いて、上記の手順により調製したＲｕＣｌ３触媒の水溶液を２６．５ｇ投入した後、更にイオン交換水２０９ｇを加え撹拌混合し、未変性のラテックス混合物（ｉ）を得た。
このときのゴム分濃度は、全配合物量１００重量％に対して、ゴム分濃度を２０重量％とした。
また、Ｒｕ濃度は、全配合物中の固形分１００重量％に対して、０．６重量％であった。
次に、得られた未変性のラテックス混合物（ｉ）をオートクレーブに投入し、オートクレーブ容器内のラテックスを窒素ガス置換してラテックス中の溶存酸素を除去した。その後、オートクレーブ内を水素ガス置換し、水素ガスを１．２ＭＰａに加圧し、８５℃になるまで急昇温し、オートクレーブ内の圧力を１．２ＭＰａに維持し、８５℃で５時間水素化反応を行った。 水素化の進行状況は、圧力の低下から判断し、圧力が１．０ＭＰａに低下すると水素を継ぎ足す方法で水素化を続行させた。５時間経過後、サンプリングし（比較例１）、その後も継続して水素化を続行させ、反応開始から２１時間経過後、オートクレーブを急冷により水素化反応を完全に停止させた。オートクレーブ内から得られた水素化天然ゴムを回収した。（比較例２）
比較例１及び比較例２で得られた水素化天然ゴムラテックスは凝集せず安定なラテックス状態であった。
得られた水素化天然ゴムラテックス中における水素化天然ゴムの水素添加率は（比較例１）１８％、（比較例２）３３％であった。
(Comparative Examples 1-2)
As a natural rubber latex of raw material, (A) Sumitomo Seika Co., Ltd. celatex 1101 (rubber content concentration 60% by weight), which is a deproteinized natural rubber latex, is charged into a 120 g beaker, and then 3 g of a surfactant After the addition, the mixture was stirred and mixed. Next, (a) 26.5 g of the aqueous solution of RuCl3 catalyst prepared by the above procedure was added using a method in which the total amount was added all at once to the raw natural rubber latex. Thereafter, 209 g of ion-exchanged water was further added and mixed by stirring to obtain an unmodified latex mixture (i).
At this time, the rubber concentration was set to 20% by weight with respect to 100% by weight of the total blend amount.
In addition, the Ru concentration was 0.6% by weight with respect to 100% by weight of the solid content in the entire formulation.
Next, the obtained unmodified latex mixture (i) was put into an autoclave, and the latex in the autoclave container was purged with nitrogen gas to remove dissolved oxygen in the latex. Thereafter, the inside of the autoclave is replaced with hydrogen gas, the hydrogen gas is pressurized to 1.2 MPa, the temperature is rapidly raised to 85 ° C., the pressure in the autoclave is maintained at 1.2 MPa, and the hydrogenation reaction is performed at 85 ° C. for 5 hours. Went. The progress of hydrogenation was judged from the decrease in pressure. When the pressure decreased to 1.0 MPa, hydrogenation was continued by adding hydrogen. After 5 hours, sampling was performed (Comparative Example 1), and the hydrogenation was continued thereafter. After 21 hours from the start of the reaction, the autoclave was quenched to completely stop the hydrogenation reaction. The hydrogenated natural rubber obtained from the autoclave was recovered. (Comparative Example 2)
The hydrogenated natural rubber latex obtained in Comparative Example 1 and Comparative Example 2 did not aggregate and was in a stable latex state.
The hydrogenation rate of the hydrogenated natural rubber in the obtained hydrogenated natural rubber latex was 18% (Comparative Example 1) and 33% (Comparative Example 2).
（比較例３〜４）
脱蛋白天然ゴムラテックスの配合量を１３３ｇ、ＲｕＣｌ３触媒の水溶液を２０ｇに変更し、ゴム分濃度を２５重量％になるようにイオン交換水の配合量を調整し、また、反応温度及び反応時間を変更した以外は比較例１と同様の方法で行った。
尚、比較例３では４時間後にサンプリングし、比較例４では反応開始から２０時間継続して水素化反応を行い、水素化天然ゴムラテックスを得た。
得られた水素化天然ゴムラテックス中における水素化天然ゴムの水素添加率は、（比較例３）１１％、（比較例４）１７％であった。
(Comparative Examples 3-4)
The amount of deproteinized natural rubber latex was changed to 133 g, the aqueous solution of RuCl3 catalyst was changed to 20 g, the amount of ion-exchanged water was adjusted so that the rubber concentration was 25% by weight, and the reaction temperature and reaction time were adjusted. The procedure was the same as in Comparative Example 1 except that the change was made.
In Comparative Example 3, sampling was performed after 4 hours, and in Comparative Example 4, hydrogenation reaction was continued for 20 hours from the start of the reaction to obtain hydrogenated natural rubber latex.
The hydrogenation rate of the hydrogenated natural rubber in the obtained hydrogenated natural rubber latex was 11% (Comparative Example 3) and 17% (Comparative Example 4).
（比較例５）
脱蛋白天然ゴムラテックスの配合量及びＲｕＣｌ３触媒水溶液の配合量を変更してゴム固形分濃度を３５重量％とし、反応温度及び反応時間を変更した以外は比較例１と同様の方法で行った。
得られた水素化天然ゴムラテックス中における水素化天然ゴムの水素添加率は、３１％であった。
(Comparative Example 5)
The same procedure as in Comparative Example 1 was carried out except that the blending amount of the deproteinized natural rubber latex and the blending amount of the RuCl3 catalyst aqueous solution were changed so that the rubber solid content concentration was 35% by weight and the reaction temperature and reaction time were changed.
The hydrogenation rate of the hydrogenated natural rubber in the obtained hydrogenated natural rubber latex was 31%.
（比較例６）
原料の天然ゴムラテックスに（Ｂ）遠心分離処理を複数回施したハイアンモニアタイプの高精製天然ゴムラテックス（マレーシア産、ゴム分濃度６０．１重量％、非ゴム分０．７重量％）を用いて１５０ｇ配合し、ＲｕＣｌ３触媒の水溶液を２５ｇに変更し、また、ゴム固形分濃度を２５重量％に変更し、反応温度及び反応時間を変更した以外は比較例１と同様の方法で行った。
得られた水素化天然ゴムラテックス中における水素化天然ゴムの水素添加率は、１５％であった。
(Comparative Example 6)
Using high-ammonia type high-purity natural rubber latex (produced in Malaysia, rubber concentration 60.1% by weight, non-rubber content 0.7% by weight) obtained by subjecting the natural rubber latex as raw material to (B) centrifugal treatment multiple times 150 g was mixed, the aqueous solution of the RuCl 3 catalyst was changed to 25 g, the rubber solid content concentration was changed to 25% by weight, and the reaction temperature and reaction time were changed, and the same procedure as in Comparative Example 1 was performed.
The hydrogenation rate of the hydrogenated natural rubber in the obtained hydrogenated natural rubber latex was 15%.
（比較例７）
原料の天然ゴムラテックスを（Ｂ）高精製天然ゴムラテックスに変更し、ゴム固形分濃度を３０重量％とし、ＲｕＣｌ３触媒水溶液の配合量を変更し、また、反応温度及び反応時間を変更した以外は比較例１と同様の方法で行った。
得られた水素化天然ゴムラテックス中における水素化天然ゴムの水素添加率は、１８％であった。
(Comparative Example 7)
The raw material natural rubber latex was changed to (B) highly purified natural rubber latex, the rubber solid content concentration was changed to 30% by weight, the blending amount of the RuCl3 catalyst aqueous solution was changed, and the reaction temperature and reaction time were changed. The same method as in Comparative Example 1 was used.
The hydrogenation rate of the hydrogenated natural rubber in the obtained hydrogenated natural rubber latex was 18%.
（比較例８）
原料の天然ゴムラテックスに（Ｃ）ハイアンモニアタイプの天然ゴムラテックスを用いて、配合量を７０ｇとし、ＲｕＣｌ３水溶液を６０ｇに変更し、ゴム固形分濃度を２５重量％に変更し、反応温度及び反応時間を変更した以外は比較例１と同様の方法で行った。
得られた水素化天然ゴムラテックス中における水素化天然ゴムの水素添加率は、１５％であった。
(Comparative Example 8)
(C) High ammonia type natural rubber latex is used as the raw natural rubber latex, the compounding amount is changed to 70 g, the RuCl3 aqueous solution is changed to 60 g, the rubber solid content concentration is changed to 25% by weight, the reaction temperature and reaction The same method as in Comparative Example 1 was performed except that the time was changed.
The hydrogenation rate of the hydrogenated natural rubber in the obtained hydrogenated natural rubber latex was 15%.
（比較例９）
触媒の添加方法を間欠的添加方法（ｂ）３回に分けて間欠的に添加する方法に変更した以外は、比較例２と同様の方法で行った。
尚、（ｂ）３回に分けて添加する方法は、予め触媒量の全量のうち１／２を原料の天然ゴムラテックスに混合し、水素化反応を４時間行った後、次いで触媒量の１／４を配合し４時間水素化反応を行い、更に残りの触媒量１／４を配合して、合計１２時間水素化反応を行った。
得られた水素化天然ゴムラテックス中における水素化天然ゴムの水素添加率は、３８％であった。
この結果より、触媒の添加方法以外を同条件で行った比較例２では水素添加率３３％に比べ、高い水素添加率であることから、間欠的に添加する方法がより好ましいことが解る。
(Comparative Example 9)
The catalyst was added in the same manner as in Comparative Example 2 except that the catalyst addition method was changed to the intermittent addition method (b) divided into three intermittent addition methods.
In addition, (b) The method of adding in 3 steps is as follows: 1/2 of the total amount of the catalyst is mixed with the natural rubber latex as a raw material in advance, the hydrogenation reaction is carried out for 4 hours, and then the catalyst amount of 1 is added. / 4 was added and the hydrogenation reaction was performed for 4 hours, and the remaining catalyst amount ¼ was further added to carry out the hydrogenation reaction for a total of 12 hours.
The hydrogenation rate of the hydrogenated natural rubber in the obtained hydrogenated natural rubber latex was 38%.
From this result, it can be seen that in Comparative Example 2 performed under the same conditions except for the catalyst addition method, the hydrogenation rate is higher than the hydrogenation rate of 33%, so that the intermittent addition method is more preferable.
（比較例１０）
触媒の添加方法を（ｂ）３回に分けて添加する方法（比較例９と同様の方法）に変更した
以外は、比較例２と同様の方法で行った。
得られた水素化天然ゴムラテックス中における水素化天然ゴムの水素添加率は、４８％であった。
(Comparative Example 10)
The catalyst was added in the same manner as in Comparative Example 2 except that the catalyst addition method was changed to (b) a method of adding the catalyst in three steps (the same method as in Comparative Example 9).
The hydrogenation rate of the hydrogenated natural rubber in the obtained hydrogenated natural rubber latex was 48%.
（比較例１１）
原料の天然ゴムラテックスに（Ｂ）高精製天然ゴムラテックスを用いて、ＲｕＣｌ３触媒の代わりに塩化パラジウム（ＲｄＣｌ２）を用いた。ＰｄＣｌ２は水に溶解し難いので、食塩を適量加えて水溶性のＰｄＣｌ２に調整し、その後、ラテックス中に混合し、比較例６と同様の方法で水素化反応を行った。
この時、Ｐｄの濃度はゴム分濃度に対して、０．４５重量％とした。
反応温度を１００℃とし、２０時間水素化反応を行ったが、反応中はオートクレーブ内の圧力低下は確認されず、殆ど水素化反応は進行しなかった。
反応後に回収した触媒含有の天然ゴムラテックスをシート化したものは、表面は非常にべたつきがあり、力学測定はできなかった。
(Comparative Example 11)
(B) Highly purified natural rubber latex was used as the raw natural rubber latex, and palladium chloride (RdCl2) was used instead of the RuCl3 catalyst. Since PdCl 2 is difficult to dissolve in water, an appropriate amount of sodium chloride was added to adjust to water-soluble PdCl 2, and then mixed in latex, and a hydrogenation reaction was performed in the same manner as in Comparative Example 6.
At this time, the concentration of Pd was 0.45% by weight with respect to the rubber concentration.
Although the reaction temperature was set to 100 ° C. and the hydrogenation reaction was carried out for 20 hours, no pressure drop in the autoclave was confirmed during the reaction, and the hydrogenation reaction hardly proceeded.
A sheet of catalyst-containing natural rubber latex recovered after the reaction had a very sticky surface, and mechanical measurements could not be performed.
（比較例１２）
原料の天然ゴムラテックスに（Ｂ）高精製天然ゴムラテックスを用いて、ＲｕＣｌ３触媒
の代わりに非水溶性のＲｕ錯体を用いた。
それをラテックス中に混合し、比較例６と同様の方法で水素化反応を行った。
この時、Ｒｕの濃度は固形分濃度に対して、０．４５重量％とした。
反応温度を１００℃とし、２０時間水素化反応を行ったが、反応中はオートクレーブ内の圧力低下は確認されず、殆ど水素化は進行しなかった。
(Comparative Example 12)
A highly purified natural rubber latex (B) was used as the raw natural rubber latex, and a water-insoluble Ru complex was used instead of the RuCl3 catalyst.
It was mixed in latex and hydrogenated by the same method as in Comparative Example 6.
At this time, the concentration of Ru was 0.45% by weight with respect to the solid content concentration.
Although the reaction temperature was set to 100 ° C. and the hydrogenation reaction was carried out for 20 hours, no pressure drop in the autoclave was confirmed during the reaction, and the hydrogenation hardly proceeded.
上記における実施例と比較例の水素化反応条件と得られた水素化天然ゴムラテックスをシート化したシートの物性値をそれぞれ表２、表３に示す。
比較例６と実施例１の比較において実施例１がより良好であり、比較例７と実施例２の比較では実施例２が良好であり、比較例８と実施例３の比較では実施例３が良好な結果である。 In comparison between Comparative Example 6 and Example 1, Example 1 is better. In comparison between Comparative Example 7 and Example 2, Example 2 is better. In comparison between Comparative Example 8 and Example 3, Example 3 is better. Is a good result.
Claims (3)
前記天然ゴムラテックス中のゴム分は、水を含む全配合物の１００重量％に対して１０重量％以上含有し、
前記水素化触媒は、水溶性ハロゲン化ルテニウム化合物であり、
連続的又は間欠的に触媒を添加することを特徴とする水素化天然ゴムラテックスの製造方法。 A hydrogenated natural rubber latex obtained by reacting natural rubber latex not subjected to deproteinization treatment with hydrogen without using an organic solvent in the presence of a hydrogenation catalyst,
The rubber content in the natural rubber latex is 10% by weight or more with respect to 100% by weight of the total formulation including water,
The hydrogenation catalyst is a water-soluble ruthenium halide compound,
A method for producing a hydrogenated natural rubber latex, wherein the catalyst is added continuously or intermittently.
The method for producing a hydrogenated natural rubber latex according to any one of claims 1 to 2 , wherein a reaction temperature of the hydrogenation reaction is 60 ° C to 150 ° C.
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