JPS58120625A - Vinyl chloride graft copolymer and its composition - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer having balanced rubber characteristics, moldability, etc., by grafting a specific amount of vinyl chloride monomer to a specific stem polymer in the presence of a small amount of a crosslinking agent. CONSTITUTION:The objective copolymer is prepared by grafting (A) vinyl chloride monomer to (B) a stem polymer composed of (i) an ethylene-vinyl acetate copolymer containing 5-60wt% vinyl acetate, (ii) an ethylene-alkyl acrylate copolymer containing 5-50wt% alkyl acrylate and/or (iii) a chlorinated ethylene polymer containing 15-49wt% chlorine, in the presence of (c) a small amount of a crosslinking agent (preferably diallyl phthalate, etc.). The amount of the vinyl chloride in the objective copolymer is selected to be 99-99.9wt%. The copolymer is compounded with (D) a plasticizer (e.g. dioctylbutyl phthalate) to obtain the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a clay vinyl graft copolymer and a composition thereof,
More specifically, at least one selected from ethylene-vinyl acetate copolymer, ethylene alkyl acrylate copolymer, and chlorinated ethylene polymer is used as a ring polymer, and the polyvinyl monomer is added to the ring polymer in the presence of a cross-linking agent. The present invention relates to an expanded vinyl grafted co-electropolymer composition containing a T-grafted copolymer and a B1 plasticizer blended therewith.

Conventionally, soft vinyl resin (1' vinyl resin, which is made by blending plasticizer with FF vinyl polymer) has been used for hoses, gaskets, electric wire fluids, etc. because it has the properties of rubber.

However, in this soft vinyl chloride resin, as the molecular weight of the expanded vinyl polymer increases, although the rubber properties improve as above, on the other hand, the moldability tends to decrease. One method for improving the processability of high molecular weight vinyl chloride polymers is to add processing aids. Although this improves processability to some extent, the improvements in physical properties due to higher molecular weight are adversely affected.

In addition, polymers obtained by polymerizing vinyl chloride monomers in the presence of a crosslinking agent tend to have a high concentration of crosslinking agent, and thus have a tendency to have a hard molding force and do not necessarily have a harsh rubber-like appearance. This is not a good strategy to maintain physical properties.

The purpose of the present invention is to solve these drawbacks, and the present invention aims to solve these shortcomings by adding at least one thermally A plastic elastomer is swollen or dissolved in a small amount of vinyl chloride monomer and grafted in the presence of a crosslinking agent to form a copolymer, and by adding a plasticizer to this, a well-balanced rubber physical property and moldability can be achieved. The present invention aims to provide a vinyl chloride polymer and a composition thereof.

That is, the first invention of the present invention is based on (1), (2),
It consists of a copolymer selected from the polymers of 1?, a vinyl chloride graft copolymer having 99tt% Y and 99.9% by weight or less, (1) an ethylene-vinyl acetate copolymer in which 5 to 60% by weight is vinyl acetate, (2) 5 to 60% by weight vinyl acetate copolymer; an ethylene-alkyl acrylate copolymer in which 50% by weight is alkyl acrylate; (3) a chlorinated ethylene polymer in which 15 to 49% by weight is chlorine; This is a vinyl chloride graft copolymer composition as a component.

The invention will be further explained in detail below.

First, the first aspect of the present invention will be explained in order. The vinyl chloride graft copolymer of the first invention is obtained by grafting a vinyl chloride monomer onto a small amount of a specific plug-type polymer in the presence of a crosslinking agent, and the vinyl chloride graft copolymer in the copolymer has 99 polymers. The thermoplastic elastomer to be made into a plug-type composite, which is characterized by a weight percent of more than 99.9 weight percent, is an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, and a chlorinated ethylene copolymer. A polymer,
Its composition is 5 to 60% by weight of vinyl acetate and ethylene-vinyl acetate in order to influence the solubility and graft copolymerizability of the polyvinyl monomer, moldability and physical properties of the resulting resin composition. Copolymer, alkyl acrylate 5-50
ft% of ethylene-alkyl acrylate copolymers and chlorinated ethylene polymers of 15 to 49 &It% of chlorine (both are one type of polymer).

The content of these thermoplastic elastomers in the vinyl chloride graphite composite of the present invention is 0.1 to 1.
Contains less than 10% of the total amount. The reason is 1f
In the case of irtqb or more, as mentioned above, the resin composition is given rubber-like physical properties such as rebound elasticity and compression set, and the melt fluidity measured by the Yuka flow tester becomes extremely good. This is because, like soft PVC, dry grain P is difficult to prepare using a mixer, and 0.1% by weight
If the amount is less than that, the effect of the present invention cannot be obtained.

The vinyl salt graft copolymer of the present invention is obtained by using a small amount of thermoplastic elastomer in the plug-type coalescence as described above and grafting it in the presence of a small amount of crosslinking agent. The resin composition obtained has elasticity Z with excellent moldability.

Further, as the polymerization method of the present invention, the corresponding polymer can be obtained by known methods such as suspension polymerization, emulsion polymerization, bulk polymerization, etc. which are commonly practiced.

To further explain Vc, pure water, dispersant,
A crosslinking agent, a thermoplastic elastomer t#57JO, and then an increased vinyl monomer may be added and polymerized.

The crosslinking agent used in the first reaction is a compound having two or more radically polymerizable functional groups in the molecule, such as ethylene glycol dimethacrylate, ethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate. , acrylics such as trimethylolpropane trimethacrylate, methacrylic acid esters, allyl esters such as diallyl phthalate, triallyl trimellitate, diallyl maleate, triallyl cyanurate, triallyl phosphate, sialyl ether, sialyl ether, etc. Among these crosslinking agents, at least one type of crosslinking agent consisting of diallyl phthalate, triallyl trimellitate, triallyl phosphate, etc. is recommended, considering the reactivity with vinyl chloride. is preferred.

The amount of addition varies depending on the type, but it is necessary to prevent the formation of delta during the polymerization reaction, and it should be in the range of 0.001 to 10000 yen per 15-nyl chloride monomer to co-exist with the desired vinyl chloride graft. It is determined together with the polymerization temperature according to the average degree of polymerization of the polymer.

If it is necessary to further adjust the average degree of polymerization, for example, saturated hydrocarbons such as n-pentane and n-hexane, chlorinated hydrocarbons such as trichlorethylene and perchlorethylene, and acetaldehyde P.

Aldehydes such as probionaldehyde, thiols such as thioglycolic acid alcohol ester, and 2-mercaptoethanol are used.

Further, for the purpose of imparting internal plasticizing ability, various monomers such as vinyl ester, vinyl ether, α-olefin, acrylic ester, and methacrylic ester may be copolymerized.

The polymerization temperature can be set arbitrarily depending on K and the amount of crosslinking agent used to obtain the desired degree of polymerization, but
Approximately 5 to 70°C is suitable.

In this way, the polymerization reaction was allowed to proceed, and the polymerization rate was 8.
When the temperature reaches 0 to 90%, the reaction does not proceed any further (therefore, unreacted vinyl chloride can be released from the system and the polymer can be taken out. The vinyl chloride graft copolymer obtained in this way is It can be used as is for hard applications.

Further, the second invention is a composition in which the vinyl chloride graft copolymer obtained in the first invention and a plasticizer are made into a V-lyblend (by using a mixer or the like), and the plasticizer is Known compounds can be used, such as dioctyl butyl phthalate, di-2-ethylhexyl phthalate, dibutyl phthalate, tricresyl phosphate, and di-2-ethylhexyl adipate.

In particular, the product of the present invention does not deteriorate molding processability (in addition, it provides a rubber-elastic ring compound that has rubber-like properties that are far better than those of conventional soft vinyl chloride resins).

In the present invention, moldability refers to tri-blendability in the step of mixing a resin and plasticizer, extrusion moldability, injection moldability, blow moldability, etc. in the molding process. Furthermore, the physical properties of rubber mean low creep properties, elongation, high impact resilience, etc., and the vinyl chloride-based graft copolymer obtained in the present invention has extremely well-balanced characteristics such as r-live blendability, moldability, and low creep properties. This is the story of the fallen tree.

As explained above, the product of the present invention is a vinyl chloride graft copolymer in which a specific thermoplastic elastomer is used as a backbone, and a vinyl chloride monomer is grafted onto this in the presence of a crosslinking agent. The physical properties of conventional high modulus vinyl chloride copolymers are those in which vinyl chloride in the polymer is more than 99 wt*v and 99.9 wt% or less, and plasticizer Y)F is blended with this, and the physical properties of conventional high elastic vinyl chloride copolymers are In addition to this, it also has excellent workability.

The present invention will be further explained below with reference to Examples, but the present invention is not limited by these.

Examples 1 to 9 180k pure water in a 6001 stainless steel autoclave
g Partially saponified polyvinyl alcohol 54.9%, crosslinking agent diallyl phthalate (DAP), ethylene-vinyl acetate copolymer (1IiVA), ethylene-ethyl acrylate copolymer (ICA), chlorinated G of ethylene polymer (CPK) was added. After evacuating the autoclave, 9 volumes of vinyl chloride wax body 't60 were charged, stirred at a temperature of 50°C for 1 hour, and 24gY of di-2-ethylhexylperoxy-dicarbonate was added to polymerize. The internal pressure of the autoclave is 4.29/cIrL.
When the temperature reached +1.G, the unreacted gas in the autoclave was discharged to the outside of the system, and one coalescence was taken out and dried. The polymerization rate was 85.

Furthermore, the content of the backbone polymer in the copolymer obtained was determined from the recovered amount. (The backbone polymer is present in the copolymer and is completely recovered.) Furthermore, the average degree of polymerization by the JZsK-6 C11 method was around 2500 in all cases.

Comparative Examples 1 to 6 Polymerization was carried out in the same manner as in Examples 1 to 9, except that the types or amounts of the backbone polymers KVA and 0-PK were changed.

Comparative Examples 7 to 10 No crosslinking agent was added, but the addition tv of the backbone polymer KVA was changed,
Stirring temperature and polymerization temperature' (carried out at 59°C, final pressure was 5
．． 6 kl! It is the same as Comparative Examples 1 to 6 except that /cm2G. The average degree of polymerization of Comparative Examples 1 to 10 is all 25.
It was around 00.

Next, for each polymer shown in Table 2, (1) ) 'live blendability, (2) roll processability, (3) Koka formula flow value, (
4) Tensile strength, elongation, and (5) aS (compression set) were evaluated by the following test methods.

(11) "Live Blend Properties 5 kg (100 parts) of each 1 combination in Table 1, 500 g (10 parts) of heavy back calcium acid, 1 Vmium stearate
50 g (5 parts) stearic acid 15 g (0.6 parts) Carzan 50 g (1 part) and di-2-ethylhexyl phthalate 3.5 kp (70 parts) v, 75! The contents of the mixture were mixed using a Henschel super mixer until the temperature of the mixture reached 110°C.

The triblendability of each polymer was evaluated from the properties of the compound cooled to about 60°C.

O: Smooth and has good tri-blend properties. Good fluidity.

×...Plasticizer is not absorbed into the skin and it does not become smooth. Liquidity is poor.

(Comparan finished in step 11) '20019'f Put it into an 8-inch roll with a surface temperature of 160℃,
Roll processability was evaluated based on the time taken for the material to wrap around the roll.

O; 0 to 60 seconds △; '51 to 60 seconds 3) roll sheet at 180℃, 50kg/cIrL
Press at 21-G for 5 minutes and punch out with a 82m thick sheet T-dumbbell.5. A tensile test was conducted according to Y Engineering SX 6723.

(5) Compression set (3) roll sheet at 190°C 100Y/σ2G 5
A test piece with a thickness of 12.7 m was prepared by pressing for 1 minute, and compression set (70°C, 22 hours) according to J Engineering SK 6301.
, compression ratio 25 cm) was measured.

According to the results in Table 2, Examples 1 to 9 are all (1).
- Good live blendability, (2) roll processability and (3)
) Koka-style flow has been significantly improved, (4) tension! Once,
It has physical property values such as elongation and (5) compression set, which are rich in good dem elasticity.

Claims (1)

[Claims] 1) At least one type of ring polymer K selected from the following polymers +11, (2) and (3), grafted with vinyl chloride monomer in the presence of a small amount of a crosslinking agent. Furthermore, the vinyl chloride in the copolymer is 99%
9.9% by weight or less of a vinyl chloride graft copolymer. (1) Ethylene-vinyl acetate copolymer containing 5 to 60% by weight of vinyl acetate. (2) Ethylene-alkyl acrylate copolymer containing 5 to 50% by weight of alkyl acrylate. (3) A chlorinated ethylene polymer containing 15 to 49% by weight of chlorine. 2) From a copolymer obtained by grafting a vinyl chloride monomer in the presence of a small amount of a crosslinking agent to at least one ring polymer selected from the following polymers (11, (2) and (3)). and an expanded vinyl graft coelectropolymer which has an expanded vinyl content in the copolymer of more than 99IIt and less than 99.9mm, and an expanded vinyl grafted coelectronic polymer whose main components are a plasticizer and a plasticizer. Composition. (1) Ethylene-vinyl acetate copolymer in which 5 to 60 weight percent is vinyl acetate. (2) Ethylene-alkyl acrylate copolymer in which 5 to 5011% is alkyl acrylate. f3) 15 to 49 It is unclear whether chlorine is an ethylene polymer or not.