JPS61157551A - Block copolymer composition - Google Patents

Abstract

PURPOSE:To provide a composition miscible uniformly with polyolefin, etc. to improve the heat-resistance, etc. of the resin, by compounding a copolymer composed mainly of a styrene-family monomer and having peroxy group with a (co)polymer having different composition from the above copolymer and free from peroxy group. CONSTITUTION:(A) 5-95wt% copolymer composed of (i) 50-98(mol)% styrene- family monomer, (ii) 1-20% fumarate monomer of formula I (R1 and R2 are 1-12C alkyl, 3-12C cycloalkyl or phenyl) and (iii) 1-20% radically copolymerizable peroxycarbonate of formula II (R3 is H or 1-4C alkyl; R4 and R5 are 1-4C alkyl; R6 is 1-12C alkyl or 3-12C cycloalkyl) is compounded with (B) 95-5wt% (co)polymer composed of one or more radically polymerizable monomer and free from the peroxycarbonate of formula II.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a copolymer A having a peroxy group in the main chain of a polymer mainly composed of a styrene monomer, and This invention relates to a block copolymer composition useful for modifying resins, etc., which is composed of (co)polymer B and (co)polymer B which have different properties and do not contain peroxy groups.

(Prior Art and Problems to be Solved by the Invention) In recent years, with the development of new technology for polymer blends, attempts to impart functional groups to polymers have been actively studied. Among them,
Polymers with peroxy groups added to their main chains are interesting materials because they have high reactivity. For example, ``Plastilant
d Kautschuk, 2 6(3) 121(1
No. 979)) has been proposed in which a peroxide having a (meth)acrylic type double bond is copolymerized with a (meth)acrylic type monomer and a peroxy group is introduced into the polymer main chain. However, since this peroxide has self-polymerizability, there have been problems with stability over time and safety.

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

Regarding this radical copolymerizable peroxycarbonate having an allyl type double bond, Japanese Patent Publication No. 57-2
6617-26619, a copolymer with vinyl chloride, JP-A-56-439514, a copolymer with ethylene-vinyl acetate, JP-A-57-5080.
Publication No. 2 proposes a copolymer with diallyl phthalate, and Japanese Patent Publication No. 57-42083 proposes a copolymer with vinyl acetate, and these copolymers have self-crosslinking properties and grafting properties. has already been confirmed.

However, when attempting to blend these copolymers with other resins, there is generally no compatibility between the resins, so grafting reactions occur locally, resulting in a decrease in the mechanical strength of the blended resin and a phase separation phenomenon. This has the disadvantage of causing deterioration of physical properties such as deterioration of appearance.

Furthermore, since the radically 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 also has the disadvantage that it does not copolymerize with monomers having conjugated double bonds such as styrene monomers.

On the other hand, in recent years, various methods for producing block copolymer compositions have been developed, in which the obtained block copolymer composition and other resins are blended, for example, under melting conditions.

Attempts have been made to produce blended resins with new properties. According to this method, large phase separation in the blend resin disappears due to the properties of the block copolymer composition, and a uniform blend resin is obtained. However, since there are no chemical bonds at the interface between the blended resins, there is a drawback that the mechanical strength of the blended resin is significantly reduced.

In order to improve these drawbacks, the present inventors previously proposed in Kokai Technical Report No. 83-6603 that the copolymer A is composed 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 strong interfacial strength between blended resins. However, since the peroxide having a double bond used is a radically copolymerizable peroxycarbonate represented by the general formula (If), the monomer composition of copolymer A is limited to vinyl acetate and vinyl chloride. Therefore, there was a drawback that it adversely affected the heat resistance, weather resistance, chemical resistance, electrical insulation properties, etc. of the blend resin. Also, (co)
Since the polymer mouth is a styrene polymer, for example, rigidity,
Although it is possible to impart surface gloss, etc., it has been 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. Knowing that all of the drawbacks could be eliminated, he completed the present invention.

That is, the present invention provides (a) 50 to 98 mol% of one or more styrenic monomers, and 1 to 20 mol% of a fumaric acid ester type monomer represented by the following general formula (I). and 5 to 95% by weight of a copolymer A comprising 1 to 20 mol% of a radically copolymerizable peroxycarbonate represented by the following general formula (n) as an essential component, and (b) one kind of radically polymerizable monomer or 2N1 or more, and has the following general formula (
The present invention relates to a block copolymer composition comprising 895 to 5% by weight of a (co)polymer not containing a radically copolymerizable peroxycarbonate represented by II).

Here, the fumaric acid ester type monomer represented by the general formula (1) is H-C-C-0-R, ...... (1) R1-
○-C-C-H (In the formula, R,, R, represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a substituted phenyl group.) It is something.

In addition, the radical copolymerizable peroxycarbonate represented by the general formula (II) is R6 ...... (U) (wherein, R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) , R,, R, represents an alkyl group having 1 to 4 carbon atoms, and R6 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms.

(Function) In the present invention, the styrene monomer in copolymer A is an essential component. This is because polymers made of styrene monomers (hereinafter abbreviated as styrene polymers) have excellent heat resistance, chemical resistance, and high electrical insulation properties.

Specific examples of the styrene monomer used include styrene, α-methylstyrene, and pt-butylstyrene.

The amount used is 50 to 98 mol%, preferably 60 to 98 mol%.
It is mole%. If it is less than 50 mol%, copolymer A loses the properties of a styrene polymer, which is not preferable.

Moreover, if it exceeds 98 mol%, the total amount of the fumaric acid ester type monomer and the radical copolymerizable peroxycarbonate will necessarily be less than 2 mol%.

If the content of the fumaric acid ester type monomer is less than 1 mol%, the copolymerizability of the radically copolymerizable peroxycarbonate will decrease, and therefore the grafting ability of the block copolymer composition will decrease, which is preferable. On the other hand, if the radical copolymerizable peroxycarbonate is less than 1 mol %, the grafting ability of the block copolymer composition naturally decreases, which is also not preferable.

Next, in copolymer A of the present invention, the fumaric acid ester type monomer represented by general formula (1) is also an essential component. Originally, the styrene monomer and the radically copolymerizable peroxycarbonate represented by the general formula (II) are not copolymerizable due to the difference in their reactivity ratio, but the above fumaric acid ester type monomer By adding a terpolymer, a terpolymer can be produced. In addition, this fumaric acid ester type monomer also has the effect of improving the heat resistance of the styrenic polymer.

Specific examples of the fumaric acid ester type monomer used include diisopropyl fumarate, di-t-butyl fumarate, dicyclohexyl fumarate, and diphenyl fumarate.

The amount used is 1 to 20% by mole in copolymer A.

Preferably it is 3 to 10 mol%. If it is less than 1 mol%, the rate of introduction of the radical copolymerizable peroxycarbonate represented by general formula (II) into copolymer A will be extremely reduced, making it impossible to obtain the desired block copolymer composition. do not have. If it exceeds 20 mol%, copolymer A loses its properties as a styrenic polymer. Furthermore, in the present invention, a radical copolymerizable peroxy represented by general formula (II), which is a component of copolymer A, Carbonate is also an essential component. This is because when this radically copolymerizable peroxycarbonate is introduced into the copolymer A, it thermally decomposes during melting, generating radicals and causing a graft reaction.

Specifically, the radical copolymerizable peroxycarbonates used include t-butylperoxyallyl carbonate, t-hexylperoxyallyl carbonate, 1,1,3.3-tetramethylbutylperoxyallyl carbonate, p-menthaneperoxy Allyl carbonate, t-butylperoxymethallyl carbonate, t-hexylperoxymethallyl carbonate, 1,
Examples include 1,3°3-tetramethylbutyl peroxymethallyl carbonate and p-menthane peroxymethallyl carbonate. Among them, preferably t-
They are butylperoxyallyl carbonate and t-hexylperoxyallyl carbonate.

The amount used is 1 to 20 mol%, preferably 2 to 10 mol%, based on copolymer A. If it is less than 1 mol %, the number of peroxy groups introduced into copolymer A will be small, and the grafting ability with other resins, which is the object of the present invention, will be weakened.

If it exceeds 20 mol%, gelation during polymerization or an extreme decrease in the molecular weight of copolymer A will occur.

In the present invention, it is also possible to add to copolymer A a radical copolymerizable monomer that is copolymerizable with the above-mentioned essential components, but the amount is such that copolymer A is It is generally preferable to limit the amount to 10 mol % or less based on the copolymer A without losing the properties.

In the present invention, there are no particular limitations on the monomer used for the (co)polymer B. This is because monomers are selected depending on the properties required for the block copolymer composition obtained by the present invention.

Generally, radically polymerizable monomers are preferred, and specifically, styrenic monomers such as styrene, α-methylstyrene, and pt-butylstyrene, acrylonitrile,
Unsaturated nitrile type monomers such as methacrylonitrile, conjugated diene type monomers such as butadiene and isoprene, unsaturated fatty acids such as acrylic acid and methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid These are (meth)acrylic acid ester type monomers such as methyl and butyl methacrylate, and α-olefin type monomers such as ethylene, propylene, and butene-1. Vinyl ester type monomers such as vinyl acetate and halogenated vinyl monomers such as pytyl chloride and vinylidene chloride can also be used, but these are not so preferred because they have drawbacks in heat resistance and weather resistance.

As a method for producing a block copolymer composition, the general formula (
The radical copolymerizable peroxycarbonate represented by If) may be produced by any method as long as it is not decomposed by a catalyst, etc. Specifically, the anion living method, sequential addition method, polymer reaction method, polymeric peroxide Examples include the azo compound method, but the most preferred is the polymeric peroxide (polymeric azo compound) method. When producing using this method, it is important to note that the selected radical copolymerizable peroxycarbonate represented by general formula (II) has a half-life temperature of 95 to 105°C for 10 hours, so the peroxy group must not be decomposed. In order to polymerize, the polymerization temperature must be set to 90°C.
The temperature should be below 85°C, more preferably below 85°C. Moreover, 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)
By confirming the presence and amount of peroxycarbonate groups by measuring the amount of active oxygen by iodometry, and by clarifying the structure of alkyl groups, cycloalkyl groups, and phenyl groups from nuclear magnetic resonance spectra, The composition can be revealed.

In addition, the block efficiency of the block copolymer composition can be measured by an extraction method or a fractional precipitation method, and the molecular weight can be determined by gel permeation chromatography (GPC).
It can be found by

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 is 5 to 95% by weight (co)
Polymer B should be 95-5% by weight. Copolymer A
is less than 5% by weight and (co)polymer B is more than 95% by weight, or if copolymer A is more than 95% by weight and (co)polymer B is less than 5% by weight, the produced block The dispersibility and dispersion stability of the copolymer composition in other resins are significantly reduced, and properties unique to block copolymers are lost, which is undesirable.

(Effects of the Invention) As detailed above, the block copolymer composition of the present invention consists of copolymer A and (co)polymer B, and copolymer A contains a styrene polymer. The block copolymer composition is characterized in that the peroxy bond is pendantly bonded in the main chain of the copolymer.

Therefore, when the block copolymer composition according to the present invention is melt-blended with another resin such as polyolefin, condensation engineering plastic, etc. as a matrix resin, the block copolymer composition is uniformly dispersed in the matrix resin, and the peroxycarbonate groups localized in the block copolymer composition are decomposed,
Since the block copolymer composition is grafted onto the matrix resin, the interfacial strength between the matrix resin and the block copolymer composition is improved, and the particle size of the block copolymer composition dispersed in the matrix resin is also improved. It gets even smaller.

Furthermore, since copolymer A contains a styrene polymer, it is expected that heat resistance, weather resistance, chemical resistance, and electrical insulation properties will be improved.

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 5 parts by weight of polymeric peroxide represented by the following formula (average degree of condensation 5 = 4.5, theoretical active oxygen amount 3.96, selected 10-hour half-life temperature 63.5°C), copolymer A and As a monomer, 85 mol% of styrene,
Diisopropyl fumarate 10 mol%, t-butyl peroxyallyl carbonate (trade name "Peromer ACJ",
(manufactured by NOF Corporation) and 100 parts by weight of a mixture consisting of 5 mol% of
0 parts by weight, suspension polymerization was carried out at a temperature of 60 to 80°C for 5 hours, and after confirming that the polymerization conversion rate was 95% or more and the polymerization was completed, the polymerization was stopped to produce copolymer A. .

Next, 100 parts by weight of methyl methacrylate was added to the copolymer A as a monomer to become the (co)polymer B,
Polymerization was continued at a polymerization temperature of 70 to 85°C, and after the polymerization was completed, 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: 0.210% Number average molecular weight: 130000 Blocking efficiency = 67% Polymerization conversion rate: 98.5% Active oxygen amount of unblocked methyl methacrylate polymer ((co)polymer B): o, o o o% The test methods include measuring the amount of active oxygen using iodometry, measuring the number average molecular weight using GPC, and using a Soxhlet extractor using acetonitrile as a solvent.
The blocking efficiency was determined by extracting the unblocked methyl methacrylate polymer, and the single polymerization conversion rate was calculated using a linear equation.

Furthermore, the heat distortion temperature of this block copolymer composition is
As a result of measurement in accordance with JIS K-7207 method, 1
The temperature was 10°C.

Comparative Example 1 In Example 1, 90 mol% of styrene and 10 mol% of diisopropyl fumarate were used as monomers to form copolymer A, except that t-butyl peroxyallyl carbonate was not added. A block copolymer composition was obtained according to Example 1. The test results were: active oxygen amount: 0.00%, number average molecular weight: 145,000, blocking efficiency: 71%, and polymerization conversion rate: 97%.

Examples 2 to 7, Comparative Examples 2 to 6 In Example 1, the composition of monomers to become copolymer A and (co)polymer B, and the composition of copolymer A and (co)polymer B
The procedure of Example 1 was repeated, except that the mixing ratio of the blocks was changed as shown in Table 1 for Examples 2 to 7, and Table 2 for Comparative Examples 2 to 6. A polymer composition was obtained.

The test results are shown in Tables 1 and 2, respectively.

In Tables 1 and 2, St: Styrene DiPF: Diisopropyl fumarate DcHF
: Dicyclohexyl fumarate TBPA: t-butyl peroxyallyl carbonate THPA: t-hexyl peroxyallyl carbonate MMA: Methyl methacrylate AN:
Furthermore, in Table 1, the block efficiency of Examples 5 and 6.7 is 150-170
It was determined by heating and crosslinking at ℃ and then extracting with benzene.

The following can be seen from the results in Table 2.

That is, in Comparative Example 2, only 0.5 mol % of DiPF is added, so the amount of active oxygen is only about 0.2% of the theoretical amount, and as in Comparative Example 3, the amount of TBPA added is 0.5 mol %. 5 mol%, the amount of active oxygen is 0.003
%, and neither of them can exhibit sufficient functionality as a block copolymer composition. In Comparative Example 4, T
Since 30 mol% of BPA is added, the number average molecular weight is extremely reduced, which is undesirable, and as in Comparative Examples 5 and 6, the blending amount of copolymer A or (co)polymer B is 2% by weight. This is not preferable because the block copolymer composition becomes a transparent solid and loses its characteristics.

Comparative Example 7 The procedure of Example 1 was followed except that the composition of the monomers to become copolymer A was 95 mol% vinyl acetate and 5 mol% t-butyl peroxyallyl carbonate. , a block copolymer composition was obtained. Its heat distortion temperature was 67°C.

Reference Example 1 As a matrix resin, 10 parts by weight of the block copolymer composition obtained in Example 1 was added to 90 parts by weight of an ethylene-vinyl acetate copolymer (trade name: Flowback 2010J, manufactured by Seitetsu Kagaku Kogyo Co., Ltd.). Add the weight part to the Banbury mixer.
The blended resins were blended in a melting state of 230° C., and the grafting efficiency, flexural modulus, and elongation of the resulting blended resin were measured.

Here, the grafting efficiency was determined by the fractional precipitation method using a benzene-acetone system, and the flexural modulus and elongation were determined by the JIS K-7203 method and JIS K-71 method, respectively.
The request was made in accordance with the 13th Act.

Grafting efficiency = 72% Flexural modulus: 350kg/cm” elongation rate
= 770% In addition, the bending elastic modulus of -2010 for flowback is 205
kg/am”, and the elongation rate was 795%.

Reference Example 2 In Reference Example 1, a blend resin was obtained by carrying out the procedure according to Reference Example 1, except that the block copolymer composition obtained in Example 1 was replaced with the one obtained in Comparative Example 1. . The measurement results of the obtained blended resin were as follows.

Grafting efficiency = 7% Flexural modulus: 250kg/am2 elongation rate
: 270%

Claims (3)

[Claims] (1) (a) One or more styrenic monomers 5
0 to 98 mol%, 1 to 20 mol% of the fumaric acid ester type monomer represented by the following general formula (I), and the following general formula (
Copolymer A5 comprising 1 to 20 mol% of the radical copolymerizable peroxycarbonate shown in II) as an essential component
~95% by weight (b) Consists of one or more radically polymerizable monomers and does not contain a radically copolymerizable peroxycarbonate represented by the following general formula (II) (co)
A block copolymer composition consisting of 95 to 5% by weight of Polymer B. The fumaric acid ester type monomer represented by the general formula (I) above has the following formulas, chemical formulas, tables, etc.
(I) (wherein R_1 and R_2 are an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group,
Indicates a substituted phenyl group. ). The radical copolymerizable peroxycarbonate represented by the above general formula (II) is as follows: ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(II) (In the formula, R_3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R_4 and R_5 are an alkyl group having 1 to 4 carbon atoms, R_
6 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms. ). (2) The block copolymer composition according to claim 1, wherein the radically copolymerizable peroxycarbonate represented by general formula (II) is t-butyl peroxyallyl carbonate. (3) The block copolymer composition according to claim 1, wherein the radically copolymerizable peroxycarbonate represented by general formula (II) is t-hexyl peroxyallyl carbonate.