JPS61287916A - Block copolymer composition - Google Patents

Abstract

PURPOSE:The titled composition excellent in heat resistance, weathering resistance, moldability and mechanical properties, comprising a copolymer having peroxy groups in a specified polymer main chain and a (co)polymer freed of peroxy groups and having a monomer composition different from that of the former. CONSTITUTION:The titled composition of an active oxygen content >=0.002wt% is obtained by block-copolymerizing 5-95wt% copolymer obtained by radical- copolymerizing 80-99.5wt% at least aromatic vinyl monomer (a) (e.g., styrene) with 0.5-20wt% radical-polymerizable peroxycarbonate (b) of the formula [wherein R1 is H or a 1-2C alkyl, R2 is H or CH3, R3-4 are each a 1-4C alkyl, R5 is a 1-12C alkyl, (alkyl-substituted) phenyl, a 3-12C cycloalkyl and n is 1-2] with 95-5wt% (co)polymer (B) comprising at least radical-(co) polymerizable monomer [e.g., (meth)acrylate ester], etc., freed of a peroxycarbonate and having a monomer composition different from that of component A at 90 deg.C or below.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a copolymer having peroxy groups in the main chain of a polymer mainly composed of one or more aromatic vinyl caramers. The present invention relates to a block copolymer composition useful for modifying resins, which is composed of A and a (co)polymer B that has a different monomer composition and does not contain peroxy groups.

In recent years, with the development of new technology for polymer blends, attempts to add functional groups to polymers have been actively investigated.

Among these, materials with peroxy groups added to the polymer main chain are very interesting materials because they have high reactivity.

(Prior art) For example, "Plastilant Color Check" (Pla
ste und Kautschuku, 26 (3)
121 (I979)), it has been proposed that a peroxide having a (meth)acrylic type double bond is copolymerized with a (meth)acrylic acid ester monomer and a peroxy group is introduced into the polymer main chain. .

Furthermore, as a similar product, Japanese Patent Publication No. 55-30790 proposes a radical copolymerizable peroxycarbonate having an allylic double bond represented by the following general formula (II).

The radical copolymerizable peroxycarbonate represented by the general formula (II) is (wherein, R6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R71R8 is an alkyl group having 1 to 4 carbon atoms, and R3 is a carbon (Indicates an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms.) The radical copolymerizable peroxycarbonate having this allylic double bond is described in Japanese Patent Publication No. 57-2
No. 6617, copolymer with vinyl chloride in Japanese Patent Publication No. 57-26619, JP-A-56-139514
In Japanese Patent Publication No. 57-50802, a copolymer with diallyl phthalate was proposed, and in Japanese Patent Publication No. 57-42083, a copolymer with vinyl acetate was proposed. ,
It has also been confirmed that these copolymers have self-crosslinking properties and grafting properties.

(Problem to be Solved by the Invention) However, when attempting to blend these copolymers with other resins, there is generally no compatibility between the resins, so a graft reaction occurs locally, causing the blended resin to This has the disadvantage of causing a decrease in mechanical strength and a decrease in physical properties due to phase separation phenomena.

Furthermore, since the radical copolymerizable peroxycarbonate represented by the general formula (n) has an allylic double bond, it has good copolymerizability with a monomer having a non-conjugated double bond. However, it has the disadvantage that it does not copolymerize with conjugated monomers, especially aromatic vinyl monomers.

Furthermore, in order to improve this drawback, attempts have been made to add or contain copolymerizable monomers, but this has resulted in the problem that it is difficult to develop the intended physical properties.

On the other hand, in recent years, methods for producing various block copolymer compositions have been developed, and blended resins with new properties are produced by blending the obtained block copolymer composition and other resins under melting conditions. Attempts are being made to manufacture According to this method, due to the properties of the block copolymer composition,
Large phase separation in the blended resin disappears and a uniform blended resin is obtained. However, since there is no chemical bond at the interface between the blend resins, there is a drawback in that the mechanical strength of the blend resin is significantly reduced.

In order to improve these drawbacks, the present inventors previously disclosed in Kokai Technical Report No. 83-6603 that the present invention consists of a copolymer (A) and a (co)polymer port, and that only the copolymer (A) contains peroxycarbonate. Block copolymer compositions into which groups have been introduced are disclosed. This block copolymer composition has excellent properties such as good dispersion stability during polymer blending and improved interfacial strength between blended resins.

However, since the peroxide having a double bond used is a radically copolymerizable peroxycarbonate represented by the above general formula ([ It is limited to monomers having a non-conjugated double bond, which has the drawback of adversely affecting the heat resistance, weather resistance, chemical resistance, electrical insulation properties, etc. of the blended resin. Furthermore, since the (co)polymer is a styrene polymer, it is possible to impart rigidity, surface gloss, etc., but it is difficult to impart impact resistance, weather resistance, etc.

(Means for Solving the Problems) The present inventors have further conducted intensive research to eliminate these conventional drawbacks, and as a result, the block copolymer composition of the present invention shown below has been developed to overcome these conventional disadvantages. The present invention was completed based on the knowledge that all the drawbacks could be eliminated.

That is, the present invention comprises (a) 80-99.5% by weight of one or more aromatic vinyl monomers and the following general formula (
Copolymer A3-95% by weight obtained by radically polymerizing 0.5-20% by weight of the radically copolymerizable peroxycarbonate represented by I), and (b) one type of radical (co)polymerizable monomer. or a (co)polymer B consisting of two or more types, containing no radically copolymerizable peroxide camibonate represented by the following general formula (I), and having a different monomer composition from the copolymer A 95- This is a block copolymer composition consisting of 5% by weight.

Here, the radical copolymerizable peroxycarbonate represented by the general formula (I) is (wherein, R1 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R2 represents a hydrogen atom or a methyl group, R3
and R4 each represent an alkyl group having 1-4 carbon atoms, R
5 represents a group selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a phenyl group, and a cycloalkyl group having 3 to 12 carbon atoms. n represents an integer of 1 to 2. ) is a compound represented by

In the present invention, the structural unit derived from the aromatic vinyl monomer in copolymer A is an essential component.

The reason is that aromatic vinyl polymers have excellent heat resistance, weather resistance,
This is because it has excellent workability.

In the present invention, the aromatic vinyl monomer used is specifically styrene, p-methylstyrene, m-
Examples include chlorostyrene and p-chlorostyrene. Preferably it is styrene.

The amount used is 80-99.5% by weight, preferably 8
5-99.5% by weight. If it is less than 80% by weight, copolymer A will lose its properties as an aromatic vinyl copolymer, which is not preferable. Furthermore, the amount of the radically copolymerizable peroxycarbonate represented by the general formula (I) necessarily exceeds 20% by weight, which is undesirable because side reactions such as gelation occur during polymerization. Moreover, if it exceeds 99.5% by weight, the radical copolymerizable peroxycarbonate represented by the general formula (I) will necessarily be less than 0.5% by weight, and this amount will cause the block copolymer composition of the present invention to The amount of active oxygen in the object is 0
．． It is less than 0.002% by weight, which is not preferable. That is,
When blending with other resins, since the amount of active oxygen is small, the grafting efficiency of the other resins and the block copolymer composition of the present invention is extremely reduced.

Furthermore, in the present invention, in copolymer A, general formula (
The radical copolymerizable peroxycarbonate represented by I) is also an essential component. This is because, when this radical copolymerizable peroxycarbonate is introduced into the copolymer A, it thermally decomposes during melting, emitting radicals, and causing a graft reaction.

Specifically, the radical copolymerizable peroxycarbonates used include t-butylperoxyacryloyloxyethyl carbonate, t-hexylperoxyacryloyloxyethyl carbonate), 1,1,3.3-
Tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-amylperoxymethacryloyloxyethyl carbonate ,
1,1.3.3-Tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, t-butylperoxyacryloyloxyethoxyethyl carbonate, t-
Hexylperoxyacryloyloxyethoxyethoxyethyl carbonate, cumylperoxyacryloyloxyethoxyethoxyethyl carbonate, t-butylperoxy'methacryloyloxyethoxyethoxyethyl carbonate, t-amylperoxymethacryloyloxyethoxyethoxyethyl carbonate, cumylperoxyacryloyloxyethoxyethoxy Ethyl carbonate, t-butylperoxyacryloyloxyisopropyl carbonate, t-hexylperoxyacryloyloxyisopropyl carbonate, L 1
．． 3.3-Tetramethylbutylperoxyacryloyloxyinpropyl carbonate, cumylperoxyacryloyloxyisopropyl carbonate, t-butylperoxymethacryloyloxyisopropyl carbonate, t-amylperoxymethacryloyloxyisopropyl carbonate, L L 3.3- Examples include tetramethylbutylperoxyacryloyloxyinpropyl carbonate and cumylperoxyacryloyloxyisopropyl carbonate. Preferably t-
Butyl acryloyloxyethyl carbonate, t-hexyl peroxy acryloyloxyethyl carbonate,
Examples include t-butylperoxymethacryloyloxyethyl carbonate, t-hexylperoxyacryloyloxyethyl carbonate, and t-butylperoxyacryloyloxyethoxyethyl carbonate.

The amount used is 0.5-20% by weight based on copolymer A.
It is. Preferably it is 1-15% by weight. When the amount is less than 0.5% by weight, the number of peroxycarbonate groups introduced into the copolymer A is small, and the amount of active oxygen in the block copolymer composition is less than 0.002% by weight. Therefore, the grafting ability with other resins, which is the object of the present invention, is not sufficiently exhibited, which is not preferable. If it exceeds 20% by weight, it is not preferable because it may cause gelation during polymerization or the copolymer A may lose the physical properties of a (meth)acrylic acid ester polymer.

In the present invention, if the monomer composition of copolymer A is different,
In particular, there are no restrictions on the monomer used for the (co)polymerization holiday. Depending on the properties required for the block copolymer composition obtained by the present invention and the purpose of modifying other resins,
This is because the monomer is selected.

In general, radically polymerizable monomers are preferred, specifically aromatic vinyl monomers such as styrene, α-methylstyrene, and p-methylstyrene, methyl (meth)acrylate, and (meth)acrylic monomers. (meth)acrylic acid ester monomers such as ethyl acid and n-butyl (meth)acrylate; vinyl esters such as vinyl acetate and vinyl propionate; 1. ! unsaturated nitrile monomers such as acrylonitrinopemethacrylonitrile, conjugated diene monomers such as bucdiene and isoprene, unsaturated fatty acid monomers such as acrylic acid and methacrylic acid, ethylene, talopyrene,
α-olefin monomers such as butene-1, vinyl chloride,
Examples include vinyl halide monomers such as vinylidene chloride.

The block copolymer composition of the present invention must have properties specific to block copolymers, such as good dispersion stability in other resins.

Therefore, the amount of copolymer A in the block copolymer composition should be 5-95% by weight and the amount of (co)polymer B should be 95-5% by weight. Copolymer A is less than 5% by weight and copolymer B is more than 95% by weight, or copolymer A is less than 9% by weight.
If the amount of (co)copolymer B exceeds 5% by weight and the amount of (co)copolymer B is less than 5% by weight, the resulting block copolymer composition will take on the properties of a homo or random (co)polymer, and other The dispersibility and dispersion stability in the resin are significantly lowered, and properties unique to block copolymers are lost, which is not preferable.

As a method for producing a block copolymer composition, the general formula (
The radical copolymerizable peroxycarbonate represented by I) may be produced by any method as long as it is not decomposed by a catalyst or the like. Specifically, the anion living method, the sequential addition method, the polymer reaction method, the polymeric peroxide (polymeric azo compound) method, etc. are exemplified, but the most preferred is the polymeric peroxide (polymeric azo compound) method. When manufactured using this method,
What should be noted is that the 10-hour half-life temperature of the radically copolymerizable peroxycarbonate represented by general formula (I) is 95-105°C, so in order to copolymerize without decomposing this peroxy group, The polymerization temperature should be below 90°C, more preferably below 85°C. Further, in that case, any method such as bulk polymerization, suspension polymerization, emulsion polymerization, or solution polymerization may be employed as the polymerization method.

The chemical structure of the copolymer A component in the block copolymer composition of the present invention has an infrared absorption spectrum (characteristic infrared absorption band)
, confirm the presence and amount of peroxycarbonate groups by measuring the amount of active oxygen by iodometry, and clarify the structures of alkyl groups, cycloalkyl groups, and phenyl groups by pyrolysis gas chromatography and nuclear magnetic resonance spectroscopy. By this, the monomer composition can be clarified.

Furthermore, the block efficiency of the block copolymer composition can be measured by extraction method and fractional precipitation method, and the molecular weight and molecular weight distribution can be measured by gel permeation chromatography (hereinafter abbreviated as GPC). be able to.

(Effects of the Invention) As detailed above, the block copolymer composition of the present invention consists of copolymer A and copolymer B, and copolymer A is an aromatic vinyl copolymer. This is a block copolymer composition characterized in that peroxide bonds are pendantly bonded in the main chain of copolymer A. Therefore, other resins, such as olefins such as polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-vinyl ester copolymers, ethylene-(meth)acrylic ester copolymers, etc. It can be used to modify condensed engineering plastics such as (co)polymers, polyphenylene ethers, polycarbonates, and thermoplastic polyesters, celluloses, and silicone resins.

In this method, the block copolymer composition of the present invention may be dissolved in a monomer during the polymerization or condensation reaction, but
Preferably, when the block copolymer composition of the present invention and another resin are melt-blended in a molding machine such as an extruder, injection molding machine, or kneading machine, a grafting reaction is preferably carried out at the same time. At this time, the melting temperature is preferably 150-300°C.

When the above operations are performed, due to the properties of the block copolymer, the block copolymer composition is uniformly dispersed in the other resin (matrix resin) and localized in the block copolymer composition. The block copolymer composition is grafted onto the matrix resin by decomposition of the peroxycarbonate groups, which improves the interfacial strength between the matrix resin and the block copolymer composition. The particle size of particles dispersed in the matrix resin also becomes smaller.

Furthermore, since copolymer A is an aromatic vinyl copolymer, it is also expected to improve heat resistance, weather resistance, and moldability.

As described above, the block copolymer composition of the present invention can be modified without reducing the mechanical properties of the matrix resin.

(Examples, Comparative Examples, and Reference Examples) The present invention will be specifically described below using Examples, Comparative Examples, and Reference Examples.

Example 1 When copolymer A was polymerized, 95% by weight of styrene was used as the aromatic vinyl monomer, and 5% by weight of t-butylperoquine methacryloylquine ethyl carbonate was used as the radical copolymerizable peroxycarbonate. They were mixed to make 100 parts by weight. Next, 5 parts by weight of a polymeric peroxide represented by the following formula 1 formula % was added as a polymerization initiator, and after thorough stirring, the temperature was lowered while stirring in a 4-hole flask equipped with a condenser containing 600 parts by weight of a 1% by weight polyvinyl alcohol aqueous solution. Suspension polymerization was carried out at 60° C.-80° C. for 5 hours, and when it was confirmed that the polymerization conversion was 95% or more and the polymerization was completed, the polymerization was stopped to obtain copolymer A.

The test results of this block copolymer composition were as follows.

Active oxygen amount 0.138% Number average molecular weight 102.000 Blocking efficiency 49% Polymerization conversion rate 98.0% Active oxygen amount of unblocked methyl methacrylate polymer (co)polymer B) 0.000% As for the test method, the amount of active oxygen was determined by iodometry, the number average molecular weight was determined by GPC measurement, and the blocking efficiency was determined by extracting the unblocked methyl methacrylate polymer using a Soxhlet extractor using acetonitrile as a solvent. I asked for it.

The polymerization conversion rate was calculated by the gravimetric method using the following formula.

The weight of the produced block copolymer composition is I x 100 The weight of all the monomers used
As a result of measurement in accordance with IS K-7207 method, 110
It was ℃.

Comparative Example 1 In Example 1, the aromatic vinyl monomer styrene was used as the monomer to form copolymer A, except that t-butylperoquine methacryloyloxyethyl carbonate was not added. , according to Example 1 to obtain a block copolymer composition. The test results were: active oxygen amount: o, ooo%, number average molecular weight: 98.000, blocking efficiency: 47%, and polymerization conversion rate: 97.5%.

Example 2-5. Comparative Example 2-5 In Example 1, the types and compositions of monomers to become copolymer A and (co)polymer B, the amount of t-butylperoxymethacryloyloxyethyl carbonate, and the The blending ratio of (co)polymer B was changed to Example 2-
Example 1 was followed except for making the changes as shown in Table 1 for Comparative Examples 5 and Table 2 for Comparative Examples 2-5, to obtain respective block copolymer compositions.

The block efficiency was measured by a fractional precipitation method in which the block copolymer composition was dissolved in benzene and then poured into petroleum ether. In addition, when copolymer B was polymerized, n-dodecyl mercaptan was used as a molecular weight regulator.

In addition, in Tables 1 and 2, t-butylperoquine methacryloyloxyethyl carbonate is M-EC,
Styrene was abbreviated as ST, methyl methacrylate as MMA, n-butyl acrylate as BA, n-butyl methacrylate as B MΔ, and acrylonitrile as ΔN.

The following can be seen from Tables 1 and 2.

That is, in Comparative Example 2, only 0.2% by weight of MBC was added to copolymer A, so the amount of active oxygen in the block copolymer composition was only 0.001%. Furthermore, in Comparative Example 3, since MBC was 30% by weight in copolymer A, gelation occurred. Also, comparative example 4,
In No. 5, the amount of copolymer A or (co)polymer B was 5% by weight or less, and when it was made into a solution, it clearly lost its properties as a block copolymer composition.

Example 6 As a result of measuring the decomposition temperature of the block copolymer composition produced in Example 1 using a thermobalance, the decomposition temperature was 230
It was ℃.

Comparative Example 6 In Example 1, vinyl acetate 9 was used as the monomer of copolymer A.
5% by weight, t-butyl peroxyallyl carbonate 5
% by weight, and a block copolymer composition was obtained in accordance with Example 1 except for the following.゛This block copolymer composition has the following properties: active oxygen content: 0.218%, number average molecular weight: 98.000, blocking efficiency: 67%, polymerization conversion rate: 98.0%.
The amount of active oxygen in polymer B) was o, ooo%, and the decomposition temperature by thermobalance was 160°C. □
Reference Example 1 As matrix Kizuki V, ethyrecytovinyl acetate copolymer [Flowback K-2010J Steel Chemical Industry Co., Ltd.
10 parts by weight of the block copolymer composition produced in Example 1 was blended with 90 parts by weight (manufactured by Co., Ltd.) for 10 minutes while melting at 230°C in a Banbury mixer, and the grafting efficiency and flexural modulus were determined. , the elongation was measured.

Incidentally, the grafting efficiency was determined by a fractional precipitation method using a benzene-acetone system.

Grafting efficiency 57% Flexural modulus 360 kg/am2 elongation rate
The flexural modulus of 750% flowback K-2010 is 205
kg/c+n2, and the elongation rate was 795%.

Reference Example 2 In the same manner as in Reference Example 1, 10 parts by weight of Flowhack K-201090 as a matrix resin and 10 parts by weight of the block copolymer composition produced in Comparative Example 1 were blended. As a result of measurement in the same manner as in Reference Example 1, graft efficiency: 5% Flexural modulus: 260 kg/cm2 Elongation rate
It was 260%.

Reference Example 3 The block copolymer composition produced in Comparative Example 2 was used, and a grafting reaction was carried out in accordance with Reference Example 1 except for the block copolymer composition. As a result, the grafting efficiency was 13%.

Claims (1)

[Claims] 1. (a) 80-99.5% by weight of one or more aromatic vinyl monomers and 0% of a radical copolymerizable peroxycarbonate represented by the following general formula (I). .5-2
Copolymer A5-9 obtained by radical copolymerization of 0% by weight
5% by weight, (b) consisting of one or more radical (co)polymerizable monomers, and containing no radical copolymerizable peroxycarbonate represented by the following general formula (I), and containing the above copolymerizable monomer. (Co)polymer B95-, which has a different monomer composition from Coalesce A
A block copolymer composition consisting of 5% by weight. The radical copolymerizable peroxycarbonate represented by the general formula (I) is as follows: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (wherein, R_1 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. , R_2 is a hydrogen atom or a methyl group, R
_3 and R_4 each represent an alkyl group having 1-4 carbon atoms, and R_5 is selected from the group consisting of an alkyl group having 1-12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, and a cycloalkyl group having 3-12 carbon atoms. Indicates the selected group. n represents an integer of 1 or 2. ) is a compound represented by 2. The block copolymer composition according to claim 1, wherein the amount of active oxygen is 0.002% by weight or more. 3. The radical copolymerizable peroxycarbonate represented by the general formula (I) is t-butylperoxymethacryloyloxyethyl carbonate, according to either claim 1 or 2. block copolymer composition. 4. The block copolymer according to any one of claims 1 to 3, wherein at least one of the aromatic vinyl monomers used in copolymer A is styrene. Coalescing composition. 5. The copolymer A is obtained by polymerizing monomers containing at least one or more (meth)acrylic acid ester monomers in an amount of 50% by weight or more. The block copolymer composition according to any one of items 1 to 4.