JPS58134135A - Method for uniformly dispersing polymer containing polar group in rubber - Google Patents

Abstract

PURPOSE:To dispersea polymer containing polar groups uniformly in a rubber, by mixing the polymer with a solution or latex of a diene type rubber in an emulsion or solution state, and adding a specific ionic dissociable sulfate to the resultant mixture. CONSTITUTION:A polymer containing polar groups is mixed with a solution or latex of a diene type rubber in an emulsion or solution state, and an ionic dissociable sulfate expressed by the formula Mx(SO4)y (M is a metal of GroupsI- VIII in the periodic table; x and y are integers corresponding to the valence) is then added to the resultant mixture. A natural polymer, e.g. protein or lignin, or a synthetic polymer, e.g. a polymer having coordinating power and hydroxyl, thiohydroxy, carbonyl, carboxyl, amino or amide groups, is used as the polymer having the polar groups.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for uniformly dispersing a polar group-containing polymer into a diene rubber. There is.

Various methods are known for dispersing polymers into diene rubber, depending on the form of the starting polymer.

(1) Solution blend (2) Latex blend (3) Tri-blend etc.

Solution blending is a method of recovering polymers by blending them together in a solution state, and if they are compatible with each other, the polymers are recovered in a relatively uniformly dispersed state.

On the other hand, known methods for coagulating latex blends include methods using acids, methods using a combination of acids and electrolytes, and methods using salts such as calcium chloride. However, they are essentially compatible with diene rubber. There is no known method for uniformly dispersing insoluble or poorly compatible polar group-containing polymers in diene rubber latex in a solution or latex state. In the triblend method, polymers containing polar groups that are insoluble or have low compatibility with rubber are not known. When blending group-containing polymers, uniform dispersion cannot be obtained even if the mixing time is increased. Improved fracture properties are expected by uniformly dispersing polar group-containing polymers in rubber. Dispersion introduces defective points into the polymer, which actually worsens the fracture properties.
The present invention was discovered @:, l', 1. ', l.

The purpose of the present invention is to provide a method for uniformly dispersing polar group-containing poly-1-, which is essentially incompatible with diene rubber or has low compatibility with diene rubber. A polymer containing a polar group is mixed into fL or in a solution state to rubber/) 5. Representation, χ and y1
The integer value corresponding to the melon value is expressed as 1'').The uniformity of the diene-based film of the polymer is the four religions that make the flow force zero for the sulfate of the ionic liquid. A distribution method is provided.

Although the reason why essentially incompatible polymers can be uniformly dispersed in the present invention has not been elucidated in detail, It is believed that the interaction of the group-containing polymer with the metal in the added 1iIIII clay lowers the cohesive force of the polar polymer itself, and that the metal is identified by the interaction with the unsaturated moiety in the diene rubber.

Therefore, the sulfate used in the present invention is preferably one that dissociates K ions, and a stable one such as barium sulfate is not preferable. US X and y are as described above), and M
For example, Has K % C@s NpA
t%83% Vs No 5WsFa, Ni%
Examples include Co. From the viewpoint of interaction with the unsaturated portion of diene rubber, industrial availability, and cost, lt%M! , Qa is preferable/still,
Sulfates may be used as a mixture of two or more.

The polar group-containing polymer used in the present invention is a natural polymer such as various proteins, carbohydrates, lipids, etc., and examples thereof include albumin, zekti, soybean protein, lignin, cellulose, and derivatives thereof.

Examples of synthetic polymers include polymers containing hydroxy groups, thiohydroxy groups, carbonyl groups, carboxyl groups, (primary to tertiary) amino groups, and amide groups.

Specifically, polyvinyl alcohol, polyvinyl acetate and saponified products thereof, polyacrylamide and copolymers thereof, vinylpyridine-containing polymers, polyvinylpyrrolidone, polyimide, polycafloractam, polyethyleneimine, amino-substituted styrene-containing V-polymers, etc. 1-, polyacrylic acid, acrylic-containing polymers, etc. ◎ Nitrogen-containing polymers are particularly preferred ・ Diene rubbers used in the present invention include polybutadiene (BR), styrene-butadiene copolymer rubber (s
s R), acrylonitrile-butadiene copolymer rubber, styrene-butadiene-acrylonitrile terpolymer rubber, polyisoprene<IA), ethylene-propylene-diene terpolymer rubber, polypentadiene and butadiene/- Examples include pentadiene copolymer rubber. When working with diene rubber in the latex state, natural polymers containing polar groups such as proteins and lignin are dissolved in water or an alkaline aqueous solution, added, and coagulated with sulfate. It will be done. Similarly, polar group-containing synthetic polymers can be made into an aqueous solution or aqueous dispersion. Na1llIl!
After uniformly dispersing this in a diene rubber solution,
Add sulfate and strip.

The amounts of alkali and soap used are not particularly limited and vary depending on the type of polar group-containing polymer. Also,
The amount of sulfate added does not need to be particularly limited, but usually
It is 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of rubber. The amount of the polar group-containing polymer added to the rubber is not particularly limited, but it is It is usually 1 to 70 parts by weight, preferably 3 to 50 parts by weight.

Example 1 Albumy Y200 flkP, I was added to latex (1- as solid rubber) of styrene-butadiene copolymer rubber (Nippon Gosei Rubber Co., Ltd. Styrene-butadiene Rubber '150G)
Dissolved in lt of water with I = 9 ・Added the solution ・After thorough stirring, the latex produced was divided into 2 parts, one of which was A.
J! ! C3OJa l〇-aqueous solution 100mj tl-
The other one was coagulated with sulfuric acid-salt according to a conventional method.

In the product coagulated with A4 (soa)a, a crumb was obtained with albumin uniformly dispersed, whereas in the acid-salt coagulated product of the comparative example, albumin phase separated and became two phases, resulting in a homogeneous product. was not obtained.

Example 2 In Example 1, instead of the styrene-butadiene copolymer rubber, a polyisogrene polymer cement (solid content of 1 or more) was used.

After emulsifying albumin 200 fvPH=9 water IAL)'decylbenzenesulfonic acid 1Off:Pflj, this was pre-blended into the above polymer cement.

The generated variance 11[ is divided into two, one of which is A4 (S04
) sl 0% aqueous solution 100 mAV addition site test 1, perform pinging. The other was coagulated with acid-salt in a conventional manner.

AL t C3Oa ) AV addition stripping gave a uniformly dispersed polymer.

On the other hand, when the sample was stripped after addition of the acid-salt, phase separation occurred and albumin was adhered to the polyisoprene layer in the form of lumps.

Example 3 Styrene/butadiene/4-vinylpyridine = 20/7
Nitrogen-containing ternary copolymer latex (solid content 200?) obtained by emulsion polymerization at a ratio of
After adding it to the solid content IKt) and stirring well to make it homogeneous, it was divided into two parts, and one part was added with 100% of an aqueous solution of A4 (sa)s, and when stripping was performed, the uniformly dispersed polymer was 〇The other side was 100ml of 10% aqueous solution of calcium chloride.
When the mixture was added and stripped, a uniform dispersion could not be obtained.

Example 4 Polyisofluorene (IR2200 from Japan Synthetic Rubber)
Polymer±ment (solid content: 1~) to solid rubber 100P
After emulsifying K with rosin soap 1OV and water,
Steam was blown in to remove the solvent, and 20 g of latex was obtained.This product contained 200 g of albumin! The solution dissolved in an alkaline aqueous solution (PH=10) was mixed and mixed uniformly using a homogenizer.

Latex WX/2 split, while KjI4 (SOa)
When 150 mtY of s l O'% aqueous solution was added, a homogeneous albumin dispersion coagulate was obtained.On the other hand, when a 2% aqueous solution IL was added to M and S, a uniform albumin dispersion coagulum was obtained.

Claims (3)

[Claims] (1) Diene rubber ** or lag group-containing polymer is mixed in an emulsified or solution state and converted to general formula m:tcs)
y C formula, where M represents a metal from Group I or Group II of the Periodic Table, and X and y represent an integer t corresponding to the valence. Method for uniformly dispersing polar group-containing polymer into diene rubber (2) The polar group-containing polymer is a polymer having a group having a coordinating power such as a hydroxy group, a thiohydroxy group, a carbonyl group, a carboxyl group, an amino group, an amide group, etc. Method 0 (3) The method according to claim 1 or 2, wherein the polar group-containing polymer is a natural protein, protein, or lignin.