JPS61287914A - 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 having an active oxygen content >=0.002wt% is obtained by block-copolymerizing 5-95wt% copolymer (A) obtained by radical-copolymerizing 80-99.5wt% at least one (meth)acrylate monomer (a) (e.g., methyl methacrylate) 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 or a 3-12C cycloalkyl and n is 1 or 2] with 95-5wt% (co)polymer (B) comprising at least one radical (co)polymerizable monomer [e.g., (alpha-methyl)styrene], etc., freed of peroxycarbonate of the formula and having a monomer composition different from that of component A at 90 deg.C or below.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a polymer having a peroxy group in the main chain containing one or more types of (meth)acrylic acid ester monomers as a main component. The present invention relates to a block copolymer composition useful for modifying resins, comprising a copolymer A and a (co)polymer B having a different monomer composition and containing no 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 <1979)), it was proposed that a peroxide having a (meth)acrylic type double bond was copolymerized with a (meth)acrylic acid ester monomer and a peroxy group was 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 (I[).

The radical copolymerizable peroxycarbonate represented by the general formula (n) is (wherein, R6 is a hydrogen atom or an alkyl having 1-4 carbon atoms/
L4, R7, Re are alkyl groups having 1-4 carbon atoms, R9
represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms. ) Regarding this radical copolymerizable peroxycarbonate r having an allyl type double bond, Japanese Patent Publication No. 57-2
6617 and JP-B No. 57-26619, copolymers with vinyl chloride, JP-A 56-39514, copolymers with ethylene-vinyl acetate, and JP-A-57-50802, copolymers with ethylene-vinyl acetate, Copolymers with vinyl acetate have been proposed in Japanese Patent Publication No. 57-42083, and it has already 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 (II) has an allyl type 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 such as aromatic vinyl polymers and (meth)acrylic acid ester 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 exhibit 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 radical copolymerizable peroxycarbonate represented by the general formula (I[), the monomer composition of copolymer A is different from that of vinyl acetate, vinyl chloride, etc. 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, in the present invention, (a) one or more types of (meth)acrylic acid ester monomers are contained in an amount of 80 to 99.5% by weight.
, 5-95% by weight of a copolymer A obtained by radically polymerizing 0.5-20% by weight of a radically copolymerizable peroxycarbonate represented by the following general formula (I), and (b> radical (co)polymerizability) from one or more monomers,
and does not contain a radical copolymerizable peroxide carbonate represented by the following general formula (I), and is composed of 95-5% by weight of a (co)polymer B having a different monomer composition from the copolymer A. It is a copolymer composition.

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 R6 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, (meth)acrylic acid in copolymer A
Building blocks derived from ester monomers are essential components. The reason is that (meth)acrylic acid ester polymers have excellent heat resistance, weather resistance, and processability. Furthermore, since (meth)acrylic acid ester polymers derived from long-chain alcohols have rubber elasticity, they are effective as impact modifiers and the like.

In the present invention, the (meth)acrylic acid ester monomer used is (meth)acrylic acid methino (meth)
Ethyl acrylate, 1-propyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate , stearyl (meth)acrylate, and the like. Preferred are methyl (meth)acrylate, ethinobe(meth)acrylate, and 2-ethylhexyl(meth)acrylate-n-butinobe(meth)acrylate.

The amount used is 80-99.5% by weight, preferably 8
It is 5-99.5 Shigesato%. If it is less than 80% by weight,
Copolymer A loses the properties of a (meth)acrylic acid ester copolymer, which is not preferable. Furthermore, necessarily general formula (I)
The radical copolymerizable peroxycarbonate represented by the formula exceeds 20% by weight, which is not preferable.

Moreover, if the amount exceeds 99.5% by weight, the general formula (I
) is less than 0.5% by weight, which is not preferable.

Furthermore, in this amount, the amount of active oxygen in the block copolymer composition of the present invention becomes 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 to generate radicals, which causes a graft reaction.

Specifically, the radical copolymerizable peroxycarbonates used include t-butylperoxyacryloyloxyethyl carbonate, 1-hexylperoxyacryloyloxyethyl carbonate, and 1.1.3.3-
Tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-amylperoxymethacryloyloxyethyl carbonate ,
L, L 3.3-Tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, t-butylperoxyacryloyloxyethoxyethyl carbonate, t
-hexylperoxyacryloyloxyethoxyethoxyethyl carbonate, cumylperoxyacryloyloxyethoxyethoxyethyl carbonate, t-butylperoxymethacryloyloxyethoxyethyl carbonate, t-amylperoxinemethacryloyloxyethoxyethoxyethyl carbonate, cumylperoxyacryloylcarbonate Roxyethoxyethyl carbonate, t-butylperoxyacryloyloxyisopropyl carbonate, t-hexylberoxyacryloyloxyisopropyl carbonate, 1.1
．． 3.3-Tetramethylbutylperoxyacryloyloxyisopropyl carbonate, cumylperoxyacryloyloxyisopropyl carbonate, t-butylperoxymethacryloyloxyisopropyl carbonate, -amylperoxymethacryloyloxyisopropyl carbonate, 1.1.3. Examples include 3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate and cumylperoxyacryloyloxyisopropyl carbonate. Preferably t-
butylacryloyloxyethyl carbonate, t-hexylperoxyacryloyloxyethyl carbonate,
Examples include t-butylperoxymethacryloyloxyethyl carbonate, t-hexylberoxymethacryloyloxyethyl carbonate, and t-butylperoxyacryloyloxyethoxyethyl carbonate.

The amount used is 0.5-20% based on copolymer A.
It is. Preferably it is 1-15% by weight. If it is less than 0.5% by weight, the amount of peroxycarbonate groups introduced into the copolymer A will be small, and the amount of active oxygen in the block copolymer composition will be 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, (meth)acrylic acid (meth)acrylic acid (meth)acrylic acid ester monomers such as ethyl and n-butyl (meth)acrylate; vinyl ester monomers such as vinyl acetate and vinyl propionate; and unsaturated nitrile monomers such as acrylonitrile. conjugated diene monomers such as butadiene and isoprene, unsaturated fatty acid monomers such as acrylic acid and methacrylic acid, α-olefin monomers such as ethylene, propylene, and butene-1, vinyl chloride, vinylidene chloride, etc. Examples include halogenated vinyl monomers.

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. When copolymer A is less than 5% by weight and (co)polymer B is more than 95% by weight, or when 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 resins will The dispersibility and dispersion stability of the block copolymer are significantly lowered, and properties specific to the block copolymer 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 using the ioton tree method, and clarify the structures of alkyl groups, cycloalkyl groups, and phenyl groups by pyrolysis gas chromatography and nuclear magnetic resonance spectroscopy. The monomer composition can be determined by

Furthermore, the blocking 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). You can ask for it.

<Effects of the Invention> As detailed above, the block copolymer composition of the present invention is composed of copolymer A and copolymer B, and copolymer A is copolymerized with (meth)acrylic acid ester. This block copolymer composition is a polymer, and is characterized in that peroxide bonds are pendantly bonded in the main chain of copolymer A. Therefore, other resins such as polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-
Olefin (co)polymers such as vinyl ester copolymers, ethylene-(meth)acrylic acid ester copolymers, condensation-based engineered plastics such as polyphenylene ether, polycarbonate, thermoplastic polyester, celluloses, silicone resins, etc. Can be used for modification.

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, the block copolymer composition may be mixed with other resins (ma) depending on the properties of the block copolymer.
The block copolymer composition is grafted onto the matrix resin by decomposition of the peroxycarbonate groups that are uniformly dispersed in J Fuchs resin and localized in the block copolymer composition. The interfacial strength between the matrix resin and the block copolymer composition is improved, and the fractional particle size of the block copolymer composition into the matrix resin is further reduced.

Furthermore, since copolymer A is a (meth)acrylic acid ester 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, methyl methacrylate 9
5% by weight and 5% by weight of t-butylperoxymethacryloyloxyethyl carbonate as a radical copolymerizable peroxycarbonate were mixed to make 100 parts by weight. Next, 5 parts by weight of a polymeric peroxide represented by the following formula % was added as a polymerization initiator, and after stirring well, the temperature was lowered in a four-hole flask equipped with a condenser containing 600 parts by weight of a 1% by weight polyvinyl alcohol aqueous solution while stirring. 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.

Next, 100 parts by weight of styrene as a monomer to become (co)polymer B was added to the suspension of copolymer A,
Polymerization was continued at a polymerization temperature of 70°C to 85°C, and after completion of the polymerization, the polymerized product was filtered, washed with water, and dried to obtain the desired block copolymer composition.

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

Active oxygen amount 0.154% Number average molecular weight 125.000 Blocking efficiency 61% Polymerization conversion rate 98.5% Unblocked styrene polymer ((co)polymer B
) Active oxygen amount o, ooo%The test method is to measure the active oxygen amount by IJ-method, GPC
The number average molecular weight was determined by measurement, and the blocking efficiency was determined by extracting unblocked polystyrene using a Soxhlet extractor using cyclohexane as a solvent.

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

The weight of the produced block copolymer composition x 100 The weight of all the monomers used Furthermore, the heat distortion temperature of this block copolymer composition is -
As a result of measurement in accordance with JIS K-7207 method, 11
It was 0°C.

Comparative Example 1 In Example 1, ★Zettai 1 was followed except that methyl methacrylate was used as the monotooth to become copolymer A and t-butylperoxymethacryloyloxyethyl carbonate was not added. A block copolymer composition was obtained. The test results were: active oxygen amount: o, ooo%, number average molecular weight: 132.000, blocking efficiency: 63%, and polymerization conversion rate: 98.5%.

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 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 polymerizing copolymer B, Example 3
In Comparative Example 4, n-dodecyl mercaptan was used as the chain transfer agent.

In addition, in Tables 1 and 2, t-butylberoxymethacryloyloxyethyl carbonate is MBC, methyl methacrylate is MMA, acrylic J-n-butyl is BA, methacrylic fJ-n-butyl is BMA, and styrene is St1. Acrylonitrile was abbreviated as AN.

From Tables 1 and 2, the following can be concluded.

That is, in Comparative Example 2, MEC in copolymer A was 0.
．． Since 2% by weight is not added, the amount of active oxygen in the block copolymer composition is only 0.001%. Furthermore, in Comparative Example 3, the content 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 The decomposition temperature of the block copolymer composition produced in Example 1 was measured using a thermobalance, and the decomposition temperature was 230°C.
Met.

Comparative Example 6 In Example 1, vinyl acetate 9 was used as the monomer of copolymer A.
5 weight i%, 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 an active oxygen content of 0.218%, a number average molecular weight of 98.000, a blocking efficiency of 67%, a polymerization conversion rate of 98.0%, and an unblocked styrene polymer ((co)polymer B).
), the amount of active oxygen was o, ooo%, and the decomposition temperature by thermobalance was 160°C.

Reference Example 1 7) As IJ Fuchs resin, the block copolymer composition produced in Example 1 was added to 90 parts by weight of ethylene-vinyl acetate copolymer (Flowback K-2010J manufactured by Steel Chemical Industry Co., Ltd.). Add 10 parts by weight to a Banbury mixer.
The mixture was melted and blended at 230° C., and its grafting efficiency, flexural modulus, and elongation were measured.

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

Grafting efficiency 67% Flexural modulus 340 kg/cm2 Elongation rate
The flexural modulus of 790% flowback K-2010 is 205
kg/cm2, and the elongation rate was 795%.

Reference Example 2 In the same manner as in Reference Example 1, 10 parts by weight of Flowback K-201090 parts by weight as +J Fuchs 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: 7% Flexural modulus: 250 kg/am2 elongation rate
It was 270%.

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 15%.

Claims (1)

[Claims] 1. (a) 80-99.5% by weight of one or more (meth)acrylic acid ester monomers and the following general formula (
Copolymer A obtained by radical copolymerization of 0.5-20% by weight of the radical copolymerizable peroxycarbonate shown in I), 5-95% by weight of (b) 1 of the radical (co)polymerizable monomer A (co)polymer B95-5 (by weight) consisting of a species or two or more species, containing no radically copolymerizable peroxycarbonate represented by the following general formula (I), and having a monomer composition different from that of the copolymer A. A block copolymer composition consisting of %. 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 to 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. Claims 1 to 3, characterized in that at least one of the (meth)acrylic acid ester monomers used in copolymer A is n-butyl acrylate. The block copolymer composition according to any one of the above. 5. Claims 1 to 3, characterized in that at least one of the (meth)acrylic acid ester monomers used in copolymer A is methyl methacrylate.
The block copolymer composition according to any one of Items. 6. Claims 1 to 3, characterized in that at least one of the (meth)acrylic acid ester monomers used in copolymer A is n-butyl methacrylate. The block copolymer composition according to any one of the above. 7. Copolymer B contains at least one aromatic vinyl monomer
7. The block copolymer composition according to any one of claims 1 to 6, which is obtained by polymerizing monomers containing 50% by weight or more of one or more species. 8. A patent claim characterized in that copolymer B is formed by polymerizing a monomer (mixture) containing at least 50% by weight of one or more (meth)acrylic acid ester monomers. A block copolymer composition according to any one of Items 1 to 6.