JPH0222763B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides 1-acetoxy-1,3-butadiene (hereinafter referred to as 1-ABD) containing a solvent-insoluble component.
The present invention relates to a composition of a polymer or copolymer (hereinafter referred to as a (co)polymer). The (co)polymer of 1-ABD is a (co)polymer of conjugated diene with a polar group, and various developments can be considered as a new polymer material.
Considering the use of this (co)polymer in adhesives, paints, etc., it is necessary to increase the adhesive strength with other materials. The present inventors have carried out intensive studies to produce a polymer suitable for use in an emulsion state as an adhesive or additive, and have found that 1-acetoxy-1, 1-acetoxy-1,
Polymer of 3-butadiene or 1-acetoxy-
A copolymer of 10% by weight or more of 1,3-butadiene and 90% by weight or less of a monomer copolymerizable with it, comprising the total number of monomer units containing 1-acetoxy-1,3-butadiene and a polar group. If the content is 70% by weight or more, use acetone as the solvent, and if the 1-acetoxy-1,3-butadiene content is less than 70% by weight, use toluene, and the solvent insoluble content when dissolved is 10 to 99% by weight. , and 90 to 1% by weight of the solvent-soluble component having a number average molecular weight of 8000 or more when dissolved.
- It was discovered that a polymer composition of acetoxy-1,3-butadiene has extremely high adhesiveness and oil resistance when used as an adhesive or paint, and also has good film forming properties. Achieved invention. That is, the present invention provides 1-acetoxy-1,3-
Polymer of butadiene or 1-acetoxy-1,
A copolymer of 10% by weight or more of 3-butadiene and 90% by weight or less of a monomer copolymerizable therewith,
- If the total content of monomer units containing acetoxy-1,3-butadiene and polar groups is 70% by weight or more, acetone is used as a solvent, and 1-acetoxy-
If the 1,3-butadiene content is less than 70% by weight, use toluene to reduce the solvent-insoluble content by 10% by weight.
-99% by weight, preferably 30-99% by weight, and 90-1% by weight of a solvent-soluble component having a number average molecular weight of 8000 or more when dissolved. A polymer composition of -acetoxy-1,3-butadiene is provided. Next, the present invention will be explained in detail. 1-ABD, which is a monomer used in the production of the 1-ABD (co)polymer composition of the present invention, can be obtained by acetoxylating butadiene in the presence of a noble metal catalyst such as palladium, or by converting crotonaldehyde into acetic anhydride and an alkali. It can be produced by heating in the presence of a metal acetate. 1-ABD obtained by these methods is a mixture of the cis form and the trans form, but the monomer of the (co)polymer of the present invention may be a mixture of the cis form or the trans form alone. Good too. Further, there is no problem even if the polymer contains impurities to the extent that they do not cause any inconvenience to the polymerization. Examples of monomers copolymerizable with 1-ABD include conjugated dienes and ethylenically unsaturated compounds. The conjugated diene is not particularly limited, but has 4 to 4 carbon atoms due to polymerizability.
The conjugated dienes of No. 6 are preferred, and among them, butadiene, isoprene, piperylene, and chloroprene are particularly preferred. As ethylenically unsaturated compounds,
Olefins having 2 to 5 carbon atoms are preferred, and ethylene is particularly preferred in terms of polymerizability. Also, acrylic acid,
Methacrylic acid and esters thereof are included in ethylenically unsaturated compounds in a broad sense, but alkyl esters of acrylic acid and methacrylic acid having 1 to 12 carbon atoms, that is, methyl esters to lauryl esters, are particularly preferred, and among them, methyl, Ethyl, propyl, n-butyl, sec-butyl, t-butyl, 2-ethylhexyl and hydroxyethyl ester are particularly preferred from the viewpoint of polymerizability. Other preferable ethylenically unsaturated compounds in terms of polymerizability are styrene,
Examples include vinyl acetate, acrylonitrile, methacrylonitrile, allyl acetate, methalylacetate, acrylamide, and methacrylamide. These copolymerizable monomers contain only one type.
-Although it may be copolymerized with ABD, it is also possible to copolymerize two or more types in combination. A preferred copolymerization composition of these copolymer monomers and 1-ABD is 1-ABD in an amount of 10 to 99.9% by weight in order to take advantage of the adhesive properties of the 1-ABD (co)polymer.
However, in order to take advantage of the characteristics of each monomer, each monomer to be copolymerized must be
It is preferably in the range of 5% to 90% by weight, more preferably 5% to 80% by weight because it further clarifies the characteristics of the monomer to be copolymerized, and more preferably 20% to 70% by weight. Further, the number average molecular weight of the solvent soluble portion of the (co)polymer composition of 1-ABD is 8000 or more, preferably
22000 or higher shows extremely excellent adhesion and oil resistance. The (co)polymer composition of the present invention is, for example, 1-
It can be obtained by emulsification or suspension polymerization of ABD alone or a monomer copolymerized with it using a surfactant, a radical polymerization initiator, a chain transfer agent, etc. As surfactants, anionic, cationic and/or nonionic surfactants can be used. As an anionic surfactant,
Examples include sulfuric esters of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, naphthalene sulfonate formalin condensates, and the like. Examples of the cationic surfactant include quaternary ammonium salts and alkylamine salts. Examples of nonionic surfactants include polyethylene glycol alkyl ester types, alkyl ether types, and alkyl phenyl ether types. It is also possible to use polyvinyl alcohol as a protective colloid. Examples of radical polymerization initiators include water-soluble radical polymerization initiators such as sodium persulfate, potassium persulfate, and ammonium persulfate, benzoyl peroxide,
Oil-soluble radical polymerization initiators such as azobisisobutyronitrile can be mentioned. Further, a redox radical polymerization initiator can also be used. Examples of the chain transfer agent include tertiary lead decyl mercaptan and carbon tetrachloride, which may be added as necessary. In addition, chelating agents,
Inorganic salts can also be used. If the polymerization is carried out at high temperatures, especially between 50 and 100 °C,
Solvent insolubilization of the produced (co)polymer proceeds from a state where the polymerization rate is low, and a component insoluble in the solvent will be present in the 1-ABD (co)polymer composition. The solvent insolubilization of this 1-ABD (co)polymer composition is
The higher the polymerization temperature and the higher the radical polymerization initiator concentration, the more likely it is to occur, and when polymerized at 50 to 100°C, 1-ABD (co-) containing any solvent-insoluble matter
Polymer compositions can be produced. In addition, the (co)polymer composition of 1-ABD with a small amount of solvent insoluble content can be used in the presence of a redox radical polymerization initiator.
It can usually be obtained by emulsion or suspension polymerization at -10 to 20°C, but for example, the reaction rate is 70°C.
By maintaining polymerization for a long time at a stage exceeding % and increasing the polymerization rate, it is also possible to produce a 1-ABD (co)polymer composition containing any solvent-insoluble matter. The 1-ABD (co)polymer composition of the present invention is
Because it contains a solvent-insoluble component and a high number average molecular weight of a solvent-soluble component, the 1-ABD (co)polymer itself has extremely high adhesion strength to glass, wood, paper, etc., and is oil resistant. It is a (co)polymer composition suitable for adhesives, paints, etc. used in an emulsion state. Note that the solvent insoluble portion described in this specification is 1-
In the composition of the (co)polymer of ABD, 1-ABD
If the total amount of monomer units containing polar groups is 70% by weight or more, use acetone as a solvent, and if it is less than 70% by weight, use toluene as a solvent, and add 1-ABD ( co)polymer 1
Part by weight was introduced, immersed at 30°C for 24 hours, stirred, and then filtered through 200 mesh gold wire, and the amount of (co)polymer remaining on the gold wire was measured. In addition, the number average molecular weight of the solvent-soluble component is determined by filtrating the 1-ABD (co)polymer after filtering off the solvent-insoluble component.
It was dissolved in tetrahydrofuran etc. and measured by GPC using polystyrene as a standard sample. The present invention will be explained in more detail below with reference to Examples. [Example 1] In a glass pressure-resistant bottle with a capacity of 500 c.c., 1-
Prepare 100 g of ABD, 6 g of sodium dodecylbenzenesulfonate, 200 g of water, 0.1 g of sodium ethylenediaminetetraacetate, 0.1 g of ferrous sulfate, 0.1 g of sodium formaldehyde sulfoxylate, and 2.0 g of paramenthane hydroperoxide.
The reaction was carried out at 15°C for 40 hours. Thereafter, 1.0 g of N,N-diethylhydroxylamine was added to stop the polymerization. As a result, an emulsion free of coagulum was obtained, and the polymerization rate was 99.9%. 100 g of this emulsion was dropped into methanol (1) to precipitate a polymer, which was thoroughly washed with methanol and then dried. 1 g of this polymer was placed in 1000 g of acetone, stirred with a magnetic stirrer at 30° C. for 24 hours, and filtered through a 200-mesh wire mesh. The acetone soluble content of the polymer is 65.7%, and the insoluble content is 34.3%.
It was in weight%. The number average molecular weight of this acetone soluble fraction was 203,000. [Comparative Example 1] Polymerization was carried out in the same manner as in Example 1, except that 1.0 g of paramenthane hydroperoxide was used and the polymerization was carried out at 10° C. for 15 hours. The acetone-insoluble content of this product is 0.2% by weight, and the soluble content is 98.8%.
The number average molecular weight of the acetone soluble fraction was 230,000. [Example 2] In a glass pressure-resistant bottle with a capacity of 500 c.c., 1-
100 g of ABD, 6 g of sodium dodecylbenzenesulfonate, 200 g of water, 0.1 g of tertiary lead decyl mercaptan, 0.2 g of sodium hydrogen sulfate,
0.2 g of potassium persulfate was charged and reacted at 60°C for 9 hours. Thereafter, 0.5 g of N,N-diethylhydroxylamine was added to stop the reaction. Polymerization rate
The number average molecular weights of the acetone-insoluble and acetone-soluble components were examined in the same manner as in Example 1, and found to be 88.3% by weight and 130,000, respectively. [Example 3] In Example 2, 1.0 g of azobisisobutyronitrile was used instead of potassium persulfate, and the temperature was 75°C.
Polymerization was carried out in the same manner as in Example 2, except that the polymerization was carried out for 9 hours. At a polymerization rate of 96%, the number average molecular weights of the acetone-insoluble and acetone-soluble components of this polymer were 88.7% by weight and 132,000, respectively. [Example 4] The emulsions obtained in Examples 1 to 3 and Comparative Example 1 were concentrated under vacuum to a solid content of 45% by weight, and these emulsions were applied to a glass plate at a rate of 100 g/m ² . After gluing the pieces together and drying them under vacuum at 50°C for 8 hours, the compression shear was measured using a Tensilon, and the results were as follows.

[Examples 5 to 8 and Comparative Example 2]

1- Polymerization was carried out in the same manner as in Example 1 except that 70 g of ABD and 30 g of styrene were used, para-menthane hydroperoxide was used as a radical polymerization initiator, and the polymerization time was as follows. The number average molecular weight of the soluble fraction was measured. The results are shown below.

[Example 9]

Polymerization was carried out in the same manner as in Example 5, using butadiene instead of styrene. The acetone-insoluble content of this copolymer was 49%, and the acetone-soluble content had a number average molecular weight of 310,000. [Example 10] Glass plates were bonded using the copolymers obtained in Examples 5 to 9 and Comparative Example 2 in the same manner as in Example 4, and the compressive shear stress was measured. The results are shown below.

【table】

Claims (1)

[Claims] 1 1-acetoxy-1,3-butadiene polymer or 1-acetoxy-1,3-butadiene 10
90% by weight or more of monomers copolymerizable with this
A copolymer with 1-acetoxy-
When the total content of monomer units containing 1,3-butadiene and polar groups is 70% by weight or more, acetone is used as the solvent, and when the 1-acetoxy-1,3-butadiene content is less than 70% by weight, toluene is used. 10 to 99% by weight of solvent-insoluble components when dissolved, and 90 to 1% by weight of solvent-soluble components having a number average molecular weight of 8000 or more,
1-acetoxy-1,
Polymer composition of 3-butadiene.