JPH0450212A - Heat-resistant resin - Google Patents

Abstract

PURPOSE:To obtain the subject resin, composed of specific three kinds of constituent components in a specific proportion, having a specified molecular weight, excellent in transparency, heat resistance and mechanical strength and useful as molded products, films, etc. CONSTITUTION:The objective resin is composed of constituent components expressed by formula I (n is 1-18) in the total amount of 50-98mol%, preferably 50-80mol% based on the whole polymer, constituent components expressed by formulas II and III (R1 is H or 1-8C alkyl ; R2 is 1-8C alkyl ; R3 is 2-8C alkyl when R1 is H and 1-8C alkyl when R1 is alkyl) in the total amount of 50-2mol%, preferably 50-20mol% based on the whole polymer further at a value of the molar ratio (formula II/formula III) of (1/99)-(99/1), preferably (30/70)-(90/10). The aforementioned resin has 1X10<3> to 5X10<6>, preferably 1X10<4> to 5X10<5> weight-average molecular weight expressed in terms of polystyrene.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to transparent heat-resistant resins.

The resin according to the present invention has excellent transparency, heat resistance, and mechanical strength, and can be used in a wide range of fields such as molded products and films.

(Prior Art) Methacrylic resins containing methyl methacrylate as a main component have been known as transparent resins and are used in a wide range of applications. However, methacrylic resin
Its applications are limited due to its low heat distortion temperature.

Maleimide copolymers have been studied in various ways because they have high heat resistance.

For example, a method of copolymerizing N-aromatically substituted maleimide with the above-mentioned methyl methacrylate,
Publication No. 1-171708 and Japanese Unexamined Patent Publication No. 62-1098
No. 11 discloses a method of copolymerizing N-aromatic substituted maleimide with a styrene resin, as described in JP-A-47-6891, JP-A-61-76512, and JP-A-6.
It is known from Japanese Patent No. 1-276807. However, although the resins obtained by these methods have better heat resistance as the N-aromatically substituted maleimide content increases, they have problems such as brittleness, poor processability, and coloring.

(Problems to be Solved by the Invention) An object of the present invention is to provide a resin with excellent transparency, heat resistance, and mechanical strength.

(Means for Solving the Problems) In view of this problem, the present inventors have made extensive studies and found that constituent component (I), constituent component (II), and constituent component (m) are present in the main chain.
It is a transparent heat-resistant resin containing the constituent component (I
) is 50 to 98 mol% of the total polymer, the total of component i) and (III) is 50 to 2 mol% of the total polymer, and the value of component (n) / (I[r) or 1 /99 to 99/1 (molar ratio) and a weight average molecular weight in terms of polystyrene of Ix103 or more and 5x106 or less has been found to satisfy the above object, and the present invention I was able to complete it.

＼　／ C+i H2m+1 (n indicates an integer from 1 to 18) CH.

-CH, -C- CH.

(n) (R1 is hydrogen or an alkyl group having 1 to 8 carbon atoms, R2 is an alkyl group having 1 to 8 carbon atoms, R5 is R1 or hydrogen,
(It is an alkyl group having 2 to 8 carbon atoms, and when R1 is an alkyl group, it is an alkyl group having 1 to 8 carbon atoms.) The compound providing component (1) is an N-alkyl-substituted maleimide; Methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-1-propylmaleimide, N-n-butylmaleimide, N-1
-Butylmaleimide, N-5-butylmaleimide, N-
t-butylmaleimide, N-n-pentylmaleimide,
Examples include Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide, and the like, and these can be used alone or in combination of two or more.

The compound providing component (n) is isobutyne;
Compounds providing component (m) include 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, 2-methyl-1-heptene, isooctene, 2
-Methyl-1-octene, 2-ethyl-1-butene, 2
-ethyl-1-bentene, 2-methyl-2-butene, 2
-Methyl-2-pentene, 2-methyl-2-hexene, etc. can be exemplified, and these can be used alone or in combination of two or more.

The content of component (I) is 50 to 98% of the total polymer.
It is mol%, preferably 50 to 90 mol%, particularly preferably 50 to 80 mol%. In addition, component (I) is 98
If it exceeds mol%, the resulting polymer will become brittle, which is not preferable.

The total content of components (II) and (m) is from 2 to 50 mol 96 of the total polymer, preferably from 10 to 50 mol %, more preferably from 20 to 50 mol %.

Furthermore, when the constituent component (m) has a linear alkyl group, such as 2-methyl-1-heptene, the flexibility tends to be excellent or the heat resistance tends to decrease; or in the case of a trisubstituted olefin such as 2-methyl-2-butene,
Although heat resistance improves, mechanical strength tends to decrease.

Therefore, in order to satisfy the purpose of the present invention, the value of component (II) / (III) should be between 1/99 and 99/1.
(molar ratio), preferably 30/70 to 90/10
(molar ratio).

Further, if necessary, other vinyl monomers can be copolymerized within a range that does not impair the purpose of the present invention. Other vinyl monomers include styrene, α-methylstyrene, vinyltoluene, 1°3-butadiene, isoprene and their halogen-substituted derivatives, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, and methacrylic acid. Methacrylic esters such as benzyl, acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, vinyl esters such as vinyl acetate, vinyl benzoate, Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, vinyl chloride, vinylidene chloride, maleic anhydride, N-phenylmaleimide, N-carboxyphenylmaleimide, acrylonitrile, ethylene, propylene, 1-butene, 2-butene and 1-
One or more compounds selected from hexene can be mentioned.

For polymerization of these monomers, any of known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be employed, but solution polymerization is particularly preferred.

Examples of the polymerization initiator include benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, t-butyl peroxyacetate, Organic peroxides such as t-butyl peroxybenzoate, or 2
,2°-azobis-(2,4-dimethylvaleronitrile)2.2'-azobis-(2-butyronitrile),2
．． 2'-azobisisobutyronitrile, dimethyl-2,
2′-azobisisobutyrate, 1,1′-azobis-
Examples include azo initiators such as (cyclohexane-1-carbonitrile).

Examples of solvents that can be used in the solution polymerization method include benzene, toluene, xylene, ethylbenzene, cyclohexane, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide, isopropyl alcohol, butyl alcohol, and the like.

The polymerization temperature can be appropriately set depending on the decomposition temperature of the initiator, but it is preferably carried out within the range of 40°C to 150°C.

Here, the weight average molecule R (Mw) of the resin produced can be determined by gel permeation chromatography (GPC). The molecular weight of the resin of the present invention is lXl
0' or more and 5 x 106 or less, especially I x 10' or more and 5
X10' or less is preferable. If the molecular weight exceeds 5 x 106, moldability will be poor, and if it is less than 1 x 103, problems such as brittleness of the resulting resin will occur.

In addition, the resin obtained in the present invention may contain hindered phenol, a heat stabilizer such as an organic phosphate ester, a benzotriazole ultraviolet absorber, a hindered amine ultraviolet stabilizer, various lubricants, various fillers, etc. as necessary. May be added.

(Effects of the Invention) The resin according to the present invention has excellent transparency, heat resistance, and mechanical strength, and is useful in a wide range of fields such as molded products and films.

(Example) The present invention will be described below with reference to Examples, but the present invention is not limited to the Examples.

The glass transition temperature (Tg) of the produced polymer was determined by Co., Ltd.
In nitrogen using Seiko electronic wave DSC200, at 10℃/
The temperature was measured at a heating rate of min.

The decomposition temperature (Td) of the produced polymer was determined at 40°C/40°C in nitrogen using Seiko Denshi Wave TG/DTA200.
The temperature was measured at a heating rate of min.

The molecular weight of the produced polymer was determined in terms of polystyrene using GPC (HLC-802A manufactured by Tosoh Corporation).

Example 1 Attachment of stirrer, nitrogen inlet pipe, thermometer and deaeration pipe 1)
g 75.08 g of N-ethylmaleimide in the autoclave
(0,6 mol), isooctene 44°84g (0,
4 mol) and 2.2°-azobisisobutyronitrile (AIBN) 0.8 g (5°0 mol), 60
The reaction was carried out at ℃ for 8 hours.

The reaction contents were poured into ethanol to precipitate the polymer. The obtained polymer was purified by reprecipitation with toluene-ethanol and then dried at 60°C under reduced pressure for 24 hours. Yield is 7
It was 9.5g.

Elemental analysis results of the obtained polymer (C; 67°4 w
t%, H: 8.7 wt%, N: 7.3 wt%) and gas chromatography analysis of the monomers remaining after polymerization, the ratio of N-ethylmaleimide, isobutyne, and isooctene in the produced polymer was 0. .510.
It was 410.1 (molar ratio). The obtained polymer had a molecular weight (Mw) of 21.7xlO' Tg - 138°C,
Td-397°C. The obtained polymer was heated to 220°C.
A sheet with a thickness of 1 mm was obtained by pressing at 5 Kg/cm2. This sheet is colorless and transparent;
No coloration was observed.

Claims (1)

[Claims] The constituent component (I) shown below accounts for 50 to 50% of the entire polymer.
98 mol%, the total amount of components (II) and (III) is 50 to 2 mol% of the entire polymer, and the value of components (II)/(III) is 1/99 to 99/1 ( molar ratio), and the weight average molecular weight in terms of polystyrene is 1 × 1
A transparent heat-resistant resin characterized in that it is 0^3 or more and 5x10^6 or less. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (n indicates an integer from 1 to 18) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (R_1 is hydrogen or an alkyl group having 1 to 8 carbon atoms, R_1 is hydrogen or an alkyl group having 1 to 8 carbon atoms,
2 is an alkyl group having 1 to 8 carbon atoms; R_3 is an alkyl group having 2 to 8 carbon atoms when R_1 is hydrogen; and when R_1 is an alkyl group, it is an alkyl group having 1 to 8 carbon atoms)