JPH03121153A - Composition containing chlorinate hydrocarbon polymer - Google Patents

Abstract

PURPOSE:To improve the transparency, impact strength, heat aging properties, and weatherability by compounding a specific chlorinated hydrocarbon polymer with a modified block copolymer. CONSTITUTION:100 pts.wt. block copolymer comprising a vinyl arom. polymer block obtd. by hydrogenating a block copolymer having a number-average mol.wt. of 20000-500000 and a mol.wt. distribution of 1.05-10 and consisting of 10-60wt.% vinyl arom. compd. and 90-40wt.% conjugated diene compd. and an olefin polymer block with an unsaturation degree of 20% or lower is reacted with 0.05-20 pts.wt. unsatd. carboxylic acid (deriv.) to give a modified block copolymer. 99-50wt.% said copolymer is compounded with 1-50wt.% at least one chlorinated hydrocarbon polymer having a mol.wt. of 10000-500000 and selected from the group consisting of polyvinyl chloride, copolymer of vinyl chloride with another monomer, and chlorinated polyethylene.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel thermoplastic polymer composition containing a chlorine-containing hydrocarbon polymer, and more particularly to a chlorine-containing hydrocarbon polymer and an unsaturated dicarboxylic acid or a derivative thereof. The present invention relates to a thermoplastic polymer composition with improved compatibility, comprising a modified vinyl aromatic compound-olefin compound block copolymer containing.

Chlorine-containing hydrocarbon polymers, especially polyvinyl chloride, are polymers with excellent tensile strength, transparency, water resistance, flame retardance, etc., and are relatively inexpensive as polymeric materials, so they are used in various molded products. It is widely used in fields such as However, polyvinyl chloride has drawbacks such as poor impact resistance, poor performance especially at low temperatures, and poor processability because the processing temperature and polymer decomposition temperature are close to each other. Therefore, it is necessary to add plasticizers such as dioctyl phthalate and dibutyl phthalate, and to use A as an impact modifier.
Various polymers such as BS resin and ethylene-vinyl acetate copolymer have been added. Compound-conjugated diene compound block copolymers have been shown to be useful as modifiers for polyvinyl chloride.

On the other hand, vinyl aromatic compound-conjugated diene compound block copolymers, particularly styrene-butadiene block copolymers, which are representative thereof, are materials that have been attracting attention in recent years. By combining,
A polymer that contains two or more polystyrene blocks and one or more polybutadiene blocks and has a relatively low styrene content exhibits properties as a thermoplastic elastomer, exhibits rubber elasticity without vulcanization, and is compatible with plastics. It is used as a material for various molding as it can be molded in a similar manner. Styrene-butadiene block copolymers with relatively high styrene content are also known as transparent impact-resistant styrenic resins.

Although attempts have already been made to improve the properties of polyvinyl chloride-based polymers and vinyl aromatic compound-conjugated diene compound block copolymers as described above, The compatibility between the polymer and the vinyl aromatic compound-conjugated diene compound block copolymer is not always satisfactory, and blends of the two generally have poor transparency and no improvement in impact resistance. The reality was that enough was enough.

The present inventors have developed a vinyl aromatic compound in which a chlorine-containing hydrocarbon polymer, of which the above-mentioned polyvinyl chloride polymer is a typical example, and an unsaturated dicarboxylic acid or a derivative thereof are combined.
We have discovered that a composition with excellent compatibility and mechanical properties such as impact resistance can be obtained from a conjugated diene compound block copolymer, and have already applied for a patent. (Japanese Patent Application No. 55-17212) As a result of further intensive studies on the composition of a chlorine-containing hydrocarbon polymer and a block copolymer, the present inventors found that a block copolymer with a low degree of unsaturation, We have discovered that by using a modified block copolymer bound with unsaturated carboxylic acids or derivatives thereof, it is possible to obtain compositions that have not only mechanical properties such as impact resistance but also excellent weather resistance and heat aging resistance, The present invention has now been completed.

That is, the present invention provides component (a); at least one chlorine-containing hydrocarbon polymer 1 to 5 selected from vinyl chloride homopolymers, copolymers of vinyl chloride and other monomers, and chlorinated polyolefins.
and (g) component: a vinyl aromatic compound polymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and a conjugated diene compound having a weight ratio in the range of 10/90 to 60/40. An unsaturated carboxylic acid or a derivative thereof is added to a block copolymer consisting of a combined block A and an olefin compound polymer block B in which the degree of unsaturation does not exceed 20%.
0.05 to 20 parts by weight of a modified block copolymer bonded thereto in an amount of 50 to 99% by weight.

The present invention will be explained in detail below.

The chlorine-containing hydrocarbon polymer, which is component (a) of the composition of the present invention, is a hydrocarbon polymer containing chlorine in its molecule, and examples thereof include vinyl chloride homopolymer; Copolymers of vinyl chloride and other heptamers, e.g.
Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-
Maleic acid ester copolymers; graft copolymers based on these; chlorinated polyolefins, such as chlorinated polyethylene, chlorinated polypropylene, and other polymers. These chlorine-containing hydrocarbon polymers generally have a molecular weight of 10,000 to 500,000, preferably 20
．． It has a molecular weight of 000 to 200,000.

In addition, the polymer of component (a), especially the polymer containing vinyl chloride, may contain dibutyl phthalate, dibutyl sebacate, diethyl carbonate, dibutylphenyl phosphate, dioctyl phthalate,
Dioctyl adipate, dioctyl phthalate, triphenyl phosphate, tricresyl phosphate, etc. can be added, and these can be blended in an amount of 1 to 100 parts by weight per 100 parts by weight of component (a).

Next, the modified block copolymer which is the component Φ) of the composition of the present invention has a small amount (one vinyl aromatic compound polymer block A and at least one olefin having an unsaturation degree not exceeding 20%). It is a modified block copolymer in which an unsaturated carboxylic acid or a derivative thereof is bonded to a block copolymer consisting of a compound polymer block B (hereinafter referred to as "base block copolymer").

Here, the olefin compound polymer block refers to monoolefins such as ethylene, propylene, and 1-butene, conjugated diolefins such as butadiene, isoprene, and 1.3-pentadiene, and 1,4-hexadiene, norbornene, norbornene derivatives, etc. It is a polymer block in which one or more olefin compounds selected from non-conjugated diolefins are polymerized or copolymerized, and the degree of unsaturation of the block is 20% or less. Therefore, when the above diolefins are used as monomers constituting a thiolefin compound polymer block, treatment is performed to reduce the degree of unsaturation by hydrogenation to the extent that the degree of unsaturation in the block portion does not exceed 20%. must be maintained. Further, a vinyl aromatic compound may be randomly copolymerized in the olefin compound polymer block. In the present invention, the "base block copolymer" is a hydrogenated block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound. The modified block copolymer used in the present invention can be produced by subjecting the above-mentioned "base block copolymer" to an addition reaction with an unsaturated carboxylic acid or a derivative thereof.

In the present invention, the modified block copolymer of component Φ) is a block copolymer (hereinafter referred to as [precursor]) composed of a vinyl aromatic compound polymer block and a polymer block mainly composed of a conjugated diene compound. The degree of unsaturation of the conjugated diene part of the block copolymer is 20%.
This is a modified block copolymer obtained by selectively hydrogenating to an extent not exceeding 100%, and then bonding an unsaturated carboxylic acid or a derivative thereof by an addition reaction.

"Block copolymer as a precursor" is at least one
2, preferably 2 or more vinyl aromatic compound polymer blocks and at least one conjugated diene-based polymer block. Here, the polymer block mainly composed of a conjugated diene has a weight ratio of a vinyl aromatic compound and a conjugated diene compound of O/100 to 50150.
．． Preferably, it is a polymer block having a composition range of O/100 to 30/70, and the distribution of the vinyl aromatic compound in this block is random, tapered (monomer component increases or decreases along the molecular chain), It may be partially block-shaped or any combination thereof. In addition, in the "block copolymer as a precursor" in the present invention, the content of the vinyl aromatic compound is contained in the transition region between the vinyl aromatic compound polymer block and the polymer block mainly composed of a conjugated diene compound. is 50% by weight
Although there may be a copolymer block of a vinyl aromatic compound and a conjugated diene compound that exceeds the above, such a polymer block is included in the above-mentioned polymer block mainly composed of a conjugated diene compound.

In the "block copolymer as a precursor", the weight ratio of the vinyl aromatic compound content to the conjugated diene compound content is preferably in the range of 10/90 to 60/40, and 1
The range of 5/85 to 55/45 exhibits properties as a thermoplastic elastic body and is suitably used as a "block copolymer as a precursor."

As the ruhinyl aromatic compound constituting the "block copolymer as a precursor", one or more kinds are selected from styrene, α-methylstyrene, vinyltoluene, etc. Among them, styrene is particularly preferred. The conjugated diene compound is selected from one or more of butadiene, isoprene, 1,3-pentadiene, etc., and butadiene and/or isoprene are particularly preferred.

The above block copolymer has a number average molecular weight of 20.000.
~soo, ooo, and the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably in the range of 1.05 to 10. In addition, the molecular structure of the block copolymer is
It may be linear, branched, radial, or a combination thereof. Furthermore, when butadiene is used as a conjugated diene compound in a block copolymer, the amount of 1°2 bonds in the microstructure of the butadiene portion is 10 to 80%.
A range of is preferred. When the modified block copolymer is particularly required to have rubber elasticity, the 1.2 bond amount is particularly preferably in the range of 35 to 55%.

In the case where the above block copolymer contains two or more vinyl aromatic compound polymer blocks or polymer blocks mainly composed of a conjugated diene compound, each block may have the same structure, or the monomer component Each structure such as content, distribution in their molecular chains, molecular weight of the block, microstructure, etc. may be different.

As a method for producing "a block copolymer as a precursor", for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43
-14979 Publication, Special Publication No. 49-36957,
Examples include methods described in Japanese Patent Publication No. 48-2423 and Japanese Patent Publication No. 48-4106. In all of these, an organic lithium compound or the like is used as an anionic polymerization initiator in a hydrocarbon solvent, and if necessary, an ether compound such as diethyl ether or tetrahydrofuran, triethylamine, N, or N is used as a vinylizing agent.

Using a tertiary amine such as N',N'-tetramethylethylenediamine, a Lewis base such as a phosphine compound such as hexamethylphosphoamide, and a polyfunctional compound such as silicon tetrachloride or epoxidized soybean oil as a coupling agent, This is a method of block copolymerizing a vinyl aromatic compound and a conjugated diene compound, and a block copolymer having a linear, branched, or radial structure is obtained.

In the present invention, any polymer obtained by any polymerization method can be used as long as it is within the above range.

Furthermore, it is also possible to use not only one type of block copolymer but also a mixture of two or more types.

By hydrogenating the above-mentioned "block copolymer as a precursor" by a known method, for example, the method described in Japanese Patent Publication No. 42-8704, a "Pro-Nc copolymer as a base material" can be obtained. . "Block copolymer as a base" is "
At least 80% of the aliphatic double bonds based on the conjugated diene compound in the polymer block based on the conjugated diene compound of the "block copolymer as a precursor" are hydrogenated, in other words, the conjugated It is necessary that the degree of unsaturation in the diene compound-based polymer block, which is morphologically converted into an olefin compound polymer block by hydrogenation, does not exceed 20%. If the degree of unsaturation of the olefin compound polymer block exceeds 20%, it is not preferable because the weather resistance and heat aging resistance of the molded article of the chlorine-containing hydrocarbon polymer composition will be poor. On the other hand, the hydrogen of the aromatic double bond based on the vinyl aromatic compound copolymerized in the vinyl aromatic compound polymer block and the vinyl aromatic compound copolymerized in the polymer block mainly composed of a conjugated diene compound as required. Although there is no particular restriction on the addition rate, it is preferable that the hydrogenation rate is 20% or less. The degree of unsaturation of the olefin compound polymer block can be measured by instrumental analysis using an infrared spectrophotometer (IR), nuclear magnetic resonance apparatus (NMR), etc., titration analysis using code titration method, etc.

The [substrate block copolymer] is then modified by an addition reaction with an unsaturated carboxylic acid or its derivative to synthesize the modified block copolymer used in the present invention. Examples of unsaturated carboxylic acids or derivatives thereof include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4=cyclohexene-1,2-dicarboxylic acid,
Endo-cis-bicyclo(2,2,13-5-heptene-2,3=dicarboxylic acid, etc., acid anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid,
Methacrylic acid, etc., esters of these monocarboxylic acids,
Examples include amides. These can be used not only alone but also as a mixture of two or more. Among these, unsaturated dicarboxylic acids or derivatives thereof are preferred, and maleic anhydride is particularly preferred.

A modified block copolymer is obtained by adding an unsaturated carboxylic acid or a derivative thereof to a "substrate block copolymer" in a solution state or a molten state, with or without the use of a radical initiator. . The method for producing these modified block copolymers is not particularly limited in the present invention, but the modified block copolymers obtained may contain undesirable components such as gel, or their melt viscosity may significantly increase, leading to processing. A manufacturing method that deteriorates properties is not preferred. A preferred method includes, for example, a method in which a "substrate block copolymer" is reacted with an unsaturated carboxylic acid or a derivative thereof in an extruder in the presence of a radical initiator.

The amount of unsaturated carboxylic acid or derivative thereof bonded to the modified block copolymer, that is, the amount of unsaturated carboxylic acid or derivative thereof added, is determined as the average value of the entire modified block copolymer used in the present invention. The number is 1 or more, preferably 3 to 200, more preferably 5 to 50, per molecule of the block copolymer. If the amount added is other than this, the properties of the thermoplastic polymer composition of the present invention will be lost. In particular, the above conditions are necessary to obtain uniformity of the polymer composition or uniform mechanical strength, impact resistance, and surface properties of the polymer composition.

The content of the bound unsaturated carboxylic acid or its derivative in the modified block copolymer can be easily determined by a method such as an infrared spectrophotometer or titration. In addition, in the present invention, the amount of unsaturated carboxylic acid or its derivative added in the modified block copolymer used as component (b) is within a range that satisfies the above range as an overall average value, and the unmodified block copolymer is may be included.

In the method for producing a modified block copolymer as described above,
Although unreacted unsaturated carboxylic acids or derivatives thereof generally remain in the modified block copolymer, these unreacted substances may be completely removed or may be left as is.

Further, in this modified block copolymer, 1,2 and 3 valent metal ions are ionicly cross-linked using the unsaturated carboxylic acid group or its derivative group bonded to the carboxylic acid or its derivative as the cross-linking position. can also be used.

The composition of the present invention is characterized by improved compatibility between components (a) and (b). (a) ingredients and (b)
The composition of the components is (a) 1 to 50% by weight, (b)
The proportion of component (b) can be any ratio within the range of 50 to 99% by weight, but a composition in which component (b) accounts for 50% by weight or more, preferably 60% by weight or more is a vinyl aromatic compound.
This is an elastomer composition in which the oil resistance, flame retardance, etc. of the olefin compound block copolymer are improved, and the compatibility of both components is good, so it can be said that it is a useful composition.

Furthermore, since the modified block copolymer used in the present invention is limited so that the degree of unsaturation of the olefin compound polymer block does not exceed 20%, conventional block copolymers with a high degree of unsaturation, such as styrene- A molded article with superior weather resistance and heat aging resistance can be obtained compared to when a butadiene block copolymer is used.

The composition of the present invention may further contain, as additives, inorganic or organic granular or fibrous fillers, various antioxidants, lubricants, viscous agents, colorants, and the like.

The composition of the present invention can be molded as a thermoplastic polymer composition by injection molding, extrusion molding, compression molding, or other molding methods.

In addition, the composition of the present invention can be used as an adhesive or pressure-sensitive adhesive in packaging materials such as sheets and films for molded products such as footwear, daily necessities, miscellaneous goods, and industrial materials, hot melts, solutions, etc.
It can be used as paint, etc.

Some examples are shown below, but these are for detailed explanation of the present invention, and it goes without saying that the scope of the present invention is not limited thereto.

Examples 1 to 4 and Comparative Examples 1 and 2 (1) Preparation of hydrogenated block copolymers N-butylurium was used as a polymerization catalyst, and butadiene and styrene were prepared in n-hexane or cyclohexane solvent using tetrahydrofuran as a vinyl content regulator. Block copolymers as shown in Table 1 were synthesized by anionic block copolymerization of .

Table 1 The vinyl content of the butadiene portion of the styrene-butadiene block copolymer was measured by the Hampton method.

Next, the block copolymers shown in Table 1 were mixed in a mixed solvent of n-hexane and cyclohexane using cobalt naphthenate and triethylaluminum as catalysts at a hydrogen pressure of 7.
Hydrogenation was performed at SCg/cfll for 5 hours at a temperature of 50°C to remove approximately 90% of the double bond in the butadiene block.
A selectively hydrogenated block copolymer was synthesized in which % of the benzene ring in the styrene block portion remained unhydrogenated. The metal remaining on the catalyst was removed by washing with an aqueous hydrochloric acid solution and methanol.

(2) Preparation of modified block copolymer For 100 parts by weight of the hydrogenated block copolymer synthesized in (1) above, 2.5 parts by weight of maleic anhydride and 0.1 parts by weight of Perhexa 25B ( After uniformly mixing the mixture (manufactured by NOF Corporation), the mixture was fed to a screw extruder (single screw, screw diameter 20si, L/D = 24, full-flight screw) under a nitrogen atmosphere, and malein was mixed at a cylinder temperature of 250°C. A chemical reaction was carried out. Unreacted maleic anhydride was removed under reduced pressure from the obtained modified block copolymer, and 0.5 parts of 2,6-theta-jazzy-butyl-4-methylphenol was added as a stabilizer per 100 parts by weight of the polymer. Part by weight was added. When this modified block copolymer was analyzed, the results shown in Table 2 were obtained.

Table 2 Modified block copolymer The amount of maleic anhydride added was measured by titration with sodium methylate.

(3) Preparation of composition Using modified block copolymer M(1), a composition containing a large amount of modified block copolymer shown in Table 3 was prepared at 175°C.
was prepared using a mixing roll.

Similarly, compositions of Comparative Examples 1 and 2 were prepared using unmodified block copolymer (1) instead of modified block copolymer M(I). Table 3 shows the bone properties of these compositions and the unmodified block copolymer (1) as a reference example.

Haze shown in Margin Table 3 below (measured with a 0.3 inch thick sheet)
and as is clear from the oil resistance values (Examples 2 and 4)
The compositions using the modified block copolymers had improved compatibility of both components compared to the compositions of Comparative Examples 1 and 2 using the corresponding unmodified block copolymers. The composition has good transparency and improved oil resistance.

Example 5 and Comparative Example 3 Using the modified block copolymer M (1) and the unmodified block copolymer (I), chlorinated polyethylene shown in Table 4 (product name: Elasrene...manufactured by Showa Denko ) were prepared by mixing in a Brabender blastograph at 200°C.

Table 4 shows the oil resistance test results of these compositions.

As is clear from the results in Table 4, the composition using the modified block copolymer of Example 5 had improved oil resistance compared to the composition of Comparative Example 3.

Margin below

Claims (1)

[Claims] 1 Component (a): at least one chlorine-containing hydrocarbon polymer selected from vinyl chloride homopolymers, copolymers of vinyl chloride and other monomers, and chlorinated polyolefins 1
~50% by weight, and component (b): a vinyl aromatic compound polymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and a conjugated diene compound with a weight ratio in the range of 10/90 to 60/40. A block copolymer consisting of a combined block A and an olefin compound polymer block B having a degree of unsaturation not exceeding 20%, and an unsaturated carboxylic acid or a derivative thereof added to the block copolymer 100
A thermoplastic polymer composition comprising 50 to 99% by weight of a modified block copolymer bound to 0.05 to 20 parts by weight per part by weight.