JPH0525252B2 - - Google Patents
Info
- Publication number
- JPH0525252B2 JPH0525252B2 JP20732685A JP20732685A JPH0525252B2 JP H0525252 B2 JPH0525252 B2 JP H0525252B2 JP 20732685 A JP20732685 A JP 20732685A JP 20732685 A JP20732685 A JP 20732685A JP H0525252 B2 JPH0525252 B2 JP H0525252B2
- Authority
- JP
- Japan
- Prior art keywords
- sugar
- compound
- water
- amino group
- molecule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920001296 polysiloxane Polymers 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 12
- 235000000346 sugar Nutrition 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 5
- -1 lactone compound Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000009102 absorption Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 5
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 235000012209 glucono delta-lactone Nutrition 0.000 description 4
- 239000000182 glucono-delta-lactone Substances 0.000 description 4
- 229960003681 gluconolactone Drugs 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 150000002596 lactones Chemical class 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WQZGKKKJIJFFOK-SVZMEOIVSA-N (+)-Galactose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-SVZMEOIVSA-N 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 2
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- UNYNVICDCJHOPO-UHFFFAOYSA-N quabalactone III Natural products CC1OC(=O)C(O)=C1C UNYNVICDCJHOPO-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 150000003334 secondary amides Chemical class 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- LGQKSQQRKHFMLI-SJYYZXOBSA-N (2s,3r,4s,5r)-2-[(3r,4r,5r,6r)-4,5,6-trihydroxyoxan-3-yl]oxyoxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@H](O)CO[C@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)OC1 LGQKSQQRKHFMLI-SJYYZXOBSA-N 0.000 description 1
- QIGJYVCQYDKYDW-UHFFFAOYSA-N 3-O-alpha-D-mannopyranosyl-D-mannopyranose Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(CO)OC(O)C1O QIGJYVCQYDKYDW-UHFFFAOYSA-N 0.000 description 1
- DBTMGCOVALSLOR-UHFFFAOYSA-N 32-alpha-galactosyl-3-alpha-galactosyl-galactose Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(OC2C(C(CO)OC(O)C2O)O)OC(CO)C1O DBTMGCOVALSLOR-UHFFFAOYSA-N 0.000 description 1
- LGQKSQQRKHFMLI-UHFFFAOYSA-N 4-O-beta-D-xylopyranosyl-beta-D-xylopyranose Natural products OC1C(O)C(O)COC1OC1C(O)C(O)C(O)OC1 LGQKSQQRKHFMLI-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- WQZGKKKJIJFFOK-WHZQZERISA-N D-aldose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-WHZQZERISA-N 0.000 description 1
- WQZGKKKJIJFFOK-IVMDWMLBSA-N D-allopyranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@@H]1O WQZGKKKJIJFFOK-IVMDWMLBSA-N 0.000 description 1
- WQZGKKKJIJFFOK-RSVSWTKNSA-N D-altro-hexose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@H](O)[C@@H]1O WQZGKKKJIJFFOK-RSVSWTKNSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FSICMNGKCHFHGP-QOKIMYEXSA-N D-maltobiono-1,5-lactone Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(=O)[C@H](O)[C@H]1O FSICMNGKCHFHGP-QOKIMYEXSA-N 0.000 description 1
- RXVWSYJTUUKTEA-UHFFFAOYSA-N D-maltotriose Natural products OC1C(O)C(OC(C(O)CO)C(O)C(O)C=O)OC(CO)C1OC1C(O)C(O)C(O)C(CO)O1 RXVWSYJTUUKTEA-UHFFFAOYSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-VANFPWTGSA-N D-mannopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-VANFPWTGSA-N 0.000 description 1
- ZCLAHGAZPPEVDX-UHFFFAOYSA-N D-panose Natural products OC1C(O)C(O)C(OC(C(O)CO)C(O)C(O)C=O)OC1COC1C(O)C(O)C(O)C(CO)O1 ZCLAHGAZPPEVDX-UHFFFAOYSA-N 0.000 description 1
- SQNRKWHRVIAKLP-UHFFFAOYSA-N D-xylobiose Natural products O=CC(O)C(O)C(CO)OC1OCC(O)C(O)C1O SQNRKWHRVIAKLP-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- AYRXSINWFIIFAE-SCLMCMATSA-N Isomaltose Natural products OC[C@H]1O[C@H](OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O)[C@@H](O)[C@@H](O)[C@@H]1O AYRXSINWFIIFAE-SCLMCMATSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- GZCGUPFRVQAUEE-ZXXMMSQZSA-N aldehydo-D-idose Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)C=O GZCGUPFRVQAUEE-ZXXMMSQZSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AEMOLEFTQBMNLQ-WAXACMCWSA-N alpha-D-glucuronic acid Chemical compound O[C@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-WAXACMCWSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- DBTMGCOVALSLOR-AXAHEAMVSA-N galactotriose Natural products OC[C@@H]1O[C@@H](O[C@@H]2[C@@H](O)[C@H](CO)O[C@@H](O[C@H]3[C@@H](O)[C@H](O)O[C@@H](CO)[C@@H]3O)[C@@H]2O)[C@H](O)[C@H](O)[C@H]1O DBTMGCOVALSLOR-AXAHEAMVSA-N 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- DLRVVLDZNNYCBX-RTPHMHGBSA-N isomaltose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)C(O)O1 DLRVVLDZNNYCBX-RTPHMHGBSA-N 0.000 description 1
- FBJQEBRMDXPWNX-FYHZSNTMSA-N isomaltotriose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](OC[C@@H]2[C@H]([C@H](O)[C@@H](O)C(O)O2)O)O1 FBJQEBRMDXPWNX-FYHZSNTMSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-CLQWQSTFSA-N l-iduronic acid Chemical compound O[C@H]1O[C@H](C(O)=O)[C@H](O)[C@@H](O)[C@@H]1O AEMOLEFTQBMNLQ-CLQWQSTFSA-N 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FYGDTMLNYKFZSV-UHFFFAOYSA-N mannotriose Natural products OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(OC2C(OC(O)C(O)C2O)CO)C(O)C1O FYGDTMLNYKFZSV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- QIGJYVCQYDKYDW-NSYYTRPSSA-N nigerose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](CO)OC(O)[C@@H]1O QIGJYVCQYDKYDW-NSYYTRPSSA-N 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- ZCLAHGAZPPEVDX-MQHGYYCBSA-N panose Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@@H](O[C@H]([C@H](O)CO)[C@H](O)[C@@H](O)C=O)O[C@@H]1CO[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 ZCLAHGAZPPEVDX-MQHGYYCBSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003267 reducing disaccharides Chemical class 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004044 tetrasaccharides Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000004043 trisaccharides Chemical class 0.000 description 1
- FYGDTMLNYKFZSV-BYLHFPJWSA-N β-1,4-galactotrioside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@H](CO)O[C@@H](O[C@@H]2[C@@H](O[C@@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-BYLHFPJWSA-N 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、１分子中に少なくとも１個の糖残基
を含有するオルガノポリシロキサン（以下糖変性
シリコーンと称する）の新規な製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel method for producing organopolysiloxane (hereinafter referred to as sugar-modified silicone) containing at least one sugar residue in one molecule.
従来、オイル状のジメチルポリシロキサン（通
称シリコーンオイル）撥、溌水性、潤滑性、光沢
付与性等の性質を有することから、離型剤、消泡
剤、艶出し剤、繊維用柔軟剤、化粧品等に応用さ
れてきた。しかしながら、シリコーンオイルは、
水と親和性を示さず、又水中に乳化され難いた
め、その使用法に制限がある。このような欠点を
改良し、かつシリコーンオイルに新しい性質を賦
与するために、長鎖アルキル基、ポリオキシアル
キレン基、アミノ基、カルボキシル基あるいはエ
ポキシ基等を導入することによる変性が行われて
いる。
Conventionally, oily dimethylpolysiloxane (commonly known as silicone oil) has properties such as repellency, water repellency, lubricity, and gloss-imparting properties, so it has been used as a mold release agent, antifoaming agent, polishing agent, fabric softener, and cosmetics. It has been applied to etc. However, silicone oil
Since it has no affinity with water and is difficult to emulsify in water, its usage is limited. In order to improve these drawbacks and impart new properties to silicone oil, modification is being carried out by introducing long-chain alkyl groups, polyoxyalkylene groups, amino groups, carboxyl groups, epoxy groups, etc. .
これらの変性シリコーンの中で、ポリオキシア
ルキレン変性シリコーンは、ジメチルポリシロキ
サンの部分を疏水基とし、ポリオキシアルキレン
部分を親水基とした非イオン系界面活性剤構造を
有しており興味深い。しかしポリオキシアルキレ
ン部分の親水性は比較的低いので、ポリオキシア
ルキレン変性シリコーンを水溶性としたり、又親
水疎水のバランスを取るためには、全体に対する
ポリオキシアルキレン部分の占める割合を高くす
る必要がある。しかしそのような場合、シリコー
ンとしての性質がポリオキシアルキレンの性質に
打ち消される恐れがある。更にポリオキシアルキ
レン変性シリコーンにはポリオキシアルキレン部
分に由来する曇点があり、使用温度が限定される
という問題がある。従つて、シリコーンオイルの
特性を有し、かつ非イオン系の親水基をバランス
よく含有した変性シリコーンの開発が望まれてい
た。
Among these modified silicones, polyoxyalkylene-modified silicones are interesting because they have a nonionic surfactant structure in which the dimethylpolysiloxane portion is a hydrophobic group and the polyoxyalkylene portion is a hydrophilic group. However, the hydrophilicity of the polyoxyalkylene moiety is relatively low, so in order to make the polyoxyalkylene-modified silicone water-soluble and to maintain a hydrophilic-hydrophobic balance, it is necessary to increase the proportion of the polyoxyalkylene moiety in the whole. be. However, in such a case, the properties of silicone may be canceled out by the properties of polyoxyalkylene. Furthermore, polyoxyalkylene-modified silicones have a cloud point originating from the polyoxyalkylene moiety, which poses the problem of limiting the temperature at which they can be used. Therefore, it has been desired to develop a modified silicone that has the characteristics of silicone oil and contains nonionic hydrophilic groups in a well-balanced manner.
上記実状に鑑み、本発明者は、ポリオキシアル
キレン基以外の非イオン性の親水基をオルガノポ
リシロキサン中に導入すべく鋭意検討した結果、
オルガノポリシロキサン中に糖残基を導入するこ
とに成功し、更に得られた糖変性シリコーンが優
れた性質を有することを見い出し本発明を完成し
た。
In view of the above-mentioned circumstances, the present inventor conducted extensive studies to introduce nonionic hydrophilic groups other than polyoxyalkylene groups into organopolysiloxane.
The present invention was completed by successfully introducing sugar residues into organopolysiloxane and by discovering that the resulting sugar-modified silicone had excellent properties.
すなわち、本発明は１分子中に少なくとも１個
の第１アミノ基を含有するオルガノポリシロキサ
ンに、アルドン酸若しくはウロン酸が分子内で脱
水環化したラクトン化合物を、当該アミノ基にお
いて反応せしめることを特徴とする１分子中に少
なくとも１個の糖残基を含有するオルガノポリシ
ロキサンの製造法を提供するものである。 That is, the present invention involves reacting an organopolysiloxane containing at least one primary amino group in one molecule with a lactone compound in which aldonic acid or uronic acid is dehydrated and cyclized within the molecule at the amino group. The present invention provides a method for producing organopolysiloxane characterized by containing at least one sugar residue in one molecule.
本発明で用いる１分子中に少なくとも１個の第
１アミノ基を含有するオルガノポリシロキサン
（以下、アミノ変性シリコーンと称する）は、直
鎖状であつても分枝鎖を有するものでもよい。含
有される第１アミノ基は、分子鎖の末端および内
部のいずれの部位に導入されていてもよい。末端
に第一アミノ基が存在しない場合、その末端はト
リオルガノシロキサンで封鎖されていても、ある
いは他のもので封鎖されていてもよい。 The organopolysiloxane containing at least one primary amino group in one molecule (hereinafter referred to as amino-modified silicone) used in the present invention may be linear or branched. The primary amino group contained may be introduced at either the terminal or internal site of the molecular chain. If a primary amino group is not present at the end, the end may be capped with a triorganosiloxane or with something else.
アルドン酸若しくはウロン酸がそれぞれ分子内
で脱水環化したラクトン化合物（以下、糖ラクト
ンと称す）としては、Ｄ−グルコース、Ｄ−ガラ
クトース、Ｄ−アロース、Ｄ−アルトロース、Ｄ
−マンノース、Ｄ−グロース、Ｄ−イドース、Ｄ
−タロースの如き還元性単糖に由来するアルドン
酸のラクトン；マルトース、セロビオース、ラク
トース、キシロビオース、イソマルトース、ニゲ
ロース、コージビオースの如き還元性二糖に由来
するアルドン酸のラクトン；マルトトリオース、
パノース、イソマルトトリオースの如き還元性三
糖に由来するアルドン酸のラクトン；四糖以上の
還元性オリゴ糖に由来するアルドン酸のラクト
ン；Ｄ−グルクロン酸、Ｌ−イズロン酸、マンヌ
ロン酸の如きウロン酸のラクトン糖があげられ
る。これらは単独あるいは混合物として用いるこ
とができる。 Examples of lactone compounds (hereinafter referred to as sugar lactones) in which aldonic acid or uronic acid are dehydrated and cyclized within the molecule include D-glucose, D-galactose, D-allose, D-altrose, and
-mannose, D-growth, D-idose, D
- Lactones of aldonic acids derived from reducing monosaccharides such as talose; lactones of aldonic acids derived from reducing disaccharides such as maltose, cellobiose, lactose, xylobiose, isomaltose, nigerose, cordibiose; maltotriose,
Lactones of aldonic acids derived from reducing trisaccharides such as panose and isomaltotriose; Lactones of aldonic acids derived from reducing oligosaccharides of tetrasaccharide or higher; D-glucuronic acid, L-iduronic acid, mannuronic acid, etc. Examples include lactone sugars of uronic acid. These can be used alone or as a mixture.
アミノ変性シリコーンと糖ラクトンとの反応
は、両者を好適には溶媒中で混合または懸濁し、
還流下撹拌しながら加熱することによつて行なう
ことができる。溶媒としては極性溶媒が好まし
く、就中メタノール、エタノール、ｎ−プロパノ
ール、イソプロパノール等の低級アルコールが好
適に使用される。なお、反応系中に水が存在する
と糖ラクトンを分解し、対応する酸を生成するの
で好ましくなく、反応系から水分を除き乾燥溶媒
を用いることが望ましい。 The reaction between amino-modified silicone and sugar lactone is carried out by mixing or suspending both preferably in a solvent,
This can be carried out by heating while stirring under reflux. As the solvent, a polar solvent is preferable, and lower alcohols such as methanol, ethanol, n-propanol, and isopropanol are particularly preferably used. Note that the presence of water in the reaction system is undesirable because it decomposes the sugar lactone and produces the corresponding acid, and it is desirable to remove water from the reaction system and use a dry solvent.
反応時間は、用いる溶媒によつて異なるが、溶
媒として低級アルコールを用いた場合、１時間程
度でも可能であるが、３〜６時間が好ましい。反
応温度は、使用する反応溶媒の還流温度が好まし
い。 The reaction time varies depending on the solvent used, but when a lower alcohol is used as the solvent, about 1 hour is possible, but 3 to 6 hours is preferable. The reaction temperature is preferably the reflux temperature of the reaction solvent used.
本発明によればオルガノポリシロキサン残基の
種類、糖残基の種類および両残基の組み合わせの
違いによつて、粘稠なオイルから粉末物質に渡る
様々な状態を示す糖変性シリコーンが得られる。
又、その糖変性シリコーンの性質も、水溶性、撥
水性いずれのものも得られる。
According to the present invention, sugar-modified silicones can be obtained that exhibit various states ranging from viscous oils to powder substances, depending on the type of organopolysiloxane residue, the type of sugar residue, and the combination of both residues. .
Furthermore, the sugar-modified silicone can be either water-soluble or water-repellent.
従つて、本発明によつて得られる糖変性シリコ
ーンは、糖残基による親水性と、オルガノポリシ
ロキサン残基による疎水性を兼ね備えた非イオン
性界面活性剤として有用であるばかりでなく、オ
ルガノポリシロキサン本来の性質を保持してお
り、化粧品原料、離型剤、防曇剤、帯電防止剤、
消泡剤、繊維油剤、プラスチツク改質剤、艶出し
剤、潤滑剤等に使用することができる。 Therefore, the sugar-modified silicone obtained by the present invention is not only useful as a nonionic surfactant that has both hydrophilicity due to sugar residues and hydrophobicity due to organopolysiloxane residues, but also as a nonionic surfactant that has both hydrophilicity due to sugar residues and hydrophobicity due to organopolysiloxane residues. It retains the original properties of siloxane, and can be used as a cosmetic raw material, mold release agent, antifogging agent, antistatic agent, etc.
It can be used in antifoaming agents, textile oils, plastic modifiers, polishing agents, lubricants, etc.
次に実施例をもつて本発明を具体的に説明する
が、本発明はこの実施例に限定されるものではな
い。
Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
実施例 １
両末端３−アミノプロピル置換ジメチルポリシ
ロキサン（チツソ株式会社製FM−3311、Mw＝
1000）20ｇ、グルコノ−δ−ラクトン８ｇ、メタ
ノール100mlの混合物を６時間還流した。メタノ
ールを減圧下留去し、残留物を水洗、次いで減圧
下乾燥することにより両末端３−グルコノアミド
プロピル置換ジメチルポリシロキサン(1)を26ｇ得
た。Example 1 Dimethylpolysiloxane substituted with 3-aminopropyl at both ends (FM-3311 manufactured by Chitsuso Corporation, M w =
1000), 8 g of glucono-δ-lactone, and 100 ml of methanol was refluxed for 6 hours. Methanol was distilled off under reduced pressure, and the residue was washed with water and then dried under reduced pressure to obtain 26 g of dimethylpolysiloxane (1) substituted with 3-gluconamidopropyl at both ends.
化合物１は白色の脆い固体であり、水を含むと
膨潤する。化合物１のIRスペクトルは3400cm-1
に糖残基の水酸基のＨ−Ｏ伸縮振動に由来する吸
収、1650cm-1に第二アミドのＣ＝Ｏ伸縮振動に由
来する吸収、1110〜1000cm-1にSi−Ｏ伸縮振動に
由来する吸収を特徴的な吸収として示した。又溶
媒としてメタノールを使用した塩酸による中和滴
定によつて化合物１中には未反応アミノ基が存在
しないことが示された。 Compound 1 is a white, brittle solid that swells when exposed to water. The IR spectrum of compound 1 is 3400 cm -1
Absorption derived from the H-O stretching vibration of the hydroxyl group of the sugar residue at 1650 cm -1 , absorption derived from the C=O stretching vibration of the secondary amide at 1110 to 1000 cm -1 , and absorption derived from the Si-O stretching vibration at 1110 to 1000 cm -1. was shown as a characteristic absorption. Further, neutralization titration with hydrochloric acid using methanol as a solvent showed that there was no unreacted amino group in Compound 1.
実施例 ２
６−アミノ−４−アザヘキシル変性ジメチルポ
リシロキサン（信越化学製KF393、アミン当量
360）50ｇ、グルコノ−δ−ラクトン13ｇ、メタ
ノール200mlの混合物を６時間還流した。メタノ
ールを減圧下留去し、残留物を水に溶解させた。
次いで反応混合物の水溶液を透析用セロフアンチ
ユーブに入れ、透析にて未反応グルコノ−δ−ラ
クトン由来のグルコン酸を除去した。次いで凍結
乾燥することにより６−グルコンアミド−４−ア
ザヘキシル変性オルガノポリシロキサン(2)を60ｇ
得た。Example 2 6-amino-4-azahexyl-modified dimethylpolysiloxane (Shin-Etsu Chemical KF393, amine equivalent
360), 13 g of glucono-δ-lactone, and 200 ml of methanol was refluxed for 6 hours. Methanol was distilled off under reduced pressure, and the residue was dissolved in water.
Next, the aqueous solution of the reaction mixture was placed in a cellophane tube for dialysis, and gluconic acid derived from unreacted glucono-δ-lactone was removed by dialysis. Then, 60 g of 6-gluconamido-4-azahexyl-modified organopolysiloxane (2) was obtained by freeze-drying.
Obtained.
化合物２は吸湿性の高い白色粉末で水溶性であ
る。化合物２のIRスペクトルは3400cm-1に糖残
基の水酸基のＨ−Ｏ伸縮振動に由来する吸収、
1650cm-1に第二アミドのＣ＝Ｏ伸縮振動に由来す
る吸収、1110〜1000cm-1にSi−Ｏ伸縮振動に由来
する吸収を特徴的な吸収として示した。溶媒とし
てメタノールを使用した塩酸による中和滴定によ
つて求めた化合物２のアミン価は62KOHmg／ｇ
であつた。メタノール中サリチルアルデヒドと反
応させたあと塩酸によつて中和滴定を行つて求め
た化合物２のアミン価（第二アミンのみに由来す
る）は61KOHmg／ｇであつた。KF393中の第一
アミノ基のみがグルコノ−δ−ラクトンと反応し
ているとした時、生成物の予想されるアミノ価は
62KOHmg／ｇである。これらの結果より以下393
中の第一アミノ基のみが反応しているといえる。 Compound 2 is a highly hygroscopic white powder and water-soluble. The IR spectrum of compound 2 shows an absorption at 3400 cm -1 originating from the H-O stretching vibration of the hydroxyl group of the sugar residue;
Characteristic absorptions were shown at 1650 cm -1 due to the C=O stretching vibration of the secondary amide, and from 1110 to 1000 cm -1 due to the Si-O stretching vibration. The amine value of compound 2 determined by neutralization titration with hydrochloric acid using methanol as a solvent is 62KOHmg/g.
It was hot. The amine value of Compound 2 (derived only from secondary amines) was 61 KOH mg/g, determined by reaction with salicylaldehyde in methanol and neutralization titration with hydrochloric acid. If only the primary amino group in KF393 is reacted with glucono-δ-lactone, the expected amino value of the product is
It is 62KOHmg/g. From these results, the following 393
It can be said that only the primary amino group inside is reacting.
実施例 ３
３−アミノプロピル変性ジメチルポリシロキサ
ン（信越化学製KF−865、アミン当量4400）50
ｇ、マルトビオノラクトン5.0ｇ、エタノール200
mlの混合物を５時間還流した。エタノールを減圧
下留去し、残留物を水洗、次いで減圧下乾燥する
ことにより３−マルトビオンアミドプロピル変性
ジメチルポリシロキサン(3)を52ｇ得た。Example 3 3-aminopropyl modified dimethylpolysiloxane (Shin-Etsu Chemical KF-865, amine equivalent 4400) 50
g, maltobionolactone 5.0g, ethanol 200g
ml of the mixture was refluxed for 5 hours. Ethanol was distilled off under reduced pressure, and the residue was washed with water and then dried under reduced pressure to obtain 52 g of 3-maltobionamidopropyl-modified dimethylpolysiloxane (3).
化合物３のIRスペクトルは実施例１の化合物
１および実施例２の化合物２のIRスペクトルと
同様、糖残基、アミド結合およびジメチルポリシ
ロキサン単位に由来する特性吸収を示した。又溶
媒としてメタノールを使用した塩酸による中和滴
定によつて化合物３中には未反応アミノ基が存在
しないことが示された。 Similar to the IR spectra of Compound 1 of Example 1 and Compound 2 of Example 2, the IR spectrum of Compound 3 showed characteristic absorption derived from sugar residues, amide bonds, and dimethylpolysiloxane units. Furthermore, neutralization titration with hydrochloric acid using methanol as a solvent showed that there was no unreacted amino group in Compound 3.
Claims (1)
含有するオルガノポリシロキサンに、アルドン酸
若しくはウロン酸が分子内で脱水環化したラクト
ン化合物を、当該アミノ基において反応せしめる
ことを特徴とする１分子中に少なくとも１個の糖
残基を含有するオルガノポリシロキサンの製造
法。1 characterized in that an organopolysiloxane containing at least one primary amino group in one molecule is reacted with a lactone compound in which an aldonic acid or a uronic acid is dehydrated and cyclized within the molecule at the amino group. A method for producing an organopolysiloxane containing at least one sugar residue in the molecule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20732685A JPS6268820A (en) | 1985-09-19 | 1985-09-19 | Production of organopolysiloxane having saccharide residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20732685A JPS6268820A (en) | 1985-09-19 | 1985-09-19 | Production of organopolysiloxane having saccharide residue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6268820A JPS6268820A (en) | 1987-03-28 |
| JPH0525252B2 true JPH0525252B2 (en) | 1993-04-12 |
Family
ID=16537904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20732685A Granted JPS6268820A (en) | 1985-09-19 | 1985-09-19 | Production of organopolysiloxane having saccharide residue |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6268820A (en) |
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-
1985
- 1985-09-19 JP JP20732685A patent/JPS6268820A/en active Granted
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Also Published As
| Publication number | Publication date |
|---|---|
| JPS6268820A (en) | 1987-03-28 |
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