JPH04332729A - Production of thermoplastic resin - Google Patents

Abstract

PURPOSE:To obtain a resin having excellent thermal and mechanical properties and useful as a matrix resin for composite material, etc., in a short time by reacting a specific aromatic polyether oligomer, etc., with a biscyclic imino ester under heating. CONSTITUTION:The objective resin is produced by the thermal reaction of (A) an aromatic polyether oligomer or polymer having hydroxyl terminal and/or amino terminal and essentially linear structure with (B) a biscyclic imino ester of formula (Q and R are direct bond or bivalent organic group) [e.g. 2,2'-bis(4,4'- dimethyl-5-oxazolone)] in the presence of a catalyst (e.g. n-butyllithium) in an inert gas atmosphere at 200-310 deg.C for 1-20min. The amount of the component B is preferably equivalent to the total hydroxyl group and the total amino group of the component A.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new method for producing thermoplastic resins. More specifically, the present invention relates to a method for producing resins with excellent thermal and mechanical properties in a very short time through rapid reaction.

0002

[Prior Art] Aromatic polyethers such as polysulfone, polyetherketone, and polyetherimide have a high secondary transition point (Tg) and excellent heat resistance, and can be applied to fibers, films, resins, etc. It is being considered. Such polyethers are generally melt-molded, but their high melt viscosity makes it difficult to impregnate the reinforcing material matrix when manufacturing complex and precise molded objects or when used as a matrix resin for composite materials. .

0003

[Object of the invention] Therefore, the present inventors have achieved
Research has been carried out with the aim of providing a method for producing polymers with excellent thermal and mechanical properties, in particular a method for producing the above polymers by so-called reaction molding, in which the polymers are reacted in a mold or in a reinforcing material matrix. Ta.

[0004] As a result, we discovered a method for obtaining a polymer with a high degree of polymerization with excellent heat resistance in an extremely short time by using a relatively low viscosity reaction raw material as a starting material.
We have arrived at the present invention.

[0005]

[Structure of the Invention] That is, the present invention heat-reacts a substantially linear aromatic polyether oligomer or polymer having a hydroxyl group terminal and/or an amino group terminal and a biscyclic imino ester. This is a method for producing thermoplastic resin characterized by the following.

The present invention will be explained in detail below.

[0007] In the present invention, a substantially linear aromatic polyether oligomer or polymer having a hydroxyl group end and/or an amino group end is used as a starting material. Here, the terminal hydroxyl group means an aliphatic hydroxyl group, an alicyclic hydroxyl group, and an aromatic hydroxyl group, and among these, an aliphatic hydroxyl group is particularly preferred. The aliphatic hydroxyl group is HO-(
CH2)n - (where n is an integer from 1 to 10)
A hydroxylalkylene group represented by is preferable.

[0008] The terminal amino group means an aliphatic amino group, an alicyclic amino group, an aromatic amino group, etc. Among these, an aliphatic amino group is particularly preferred. The aliphatic amino group is H2N-(CH2)n-(where n is 1
It is an integer between ~10. ) is preferred.

In the present invention, the main chain of the aromatic polyether oligomer or polymer is an aromatic group, preferably phenylene or naphthylene, in addition to an ether group, a sulfone group, a ketone group, an imide group, a sulfide group, etc. Examples of such polymers include so-called polyarylene ether, polyether sulfone, polyether ketone, and polyetherimide. Further, the oligomer or polymer here needs to be substantially linear, and if it is highly branched, the mechanical properties of the final molded product obtained will be poor, which is not preferable.

[0010] In the present invention, oligomers or polymers having the aforementioned hydroxyl group and/or amino group, preferably an aliphatic hydroxyl group and/or aliphatic amino group, at the terminal are used. Such oligomers or polymers having hydroxyl group terminals and/or amino group terminals can be produced using various conventionally known chemical reactions.

For example, oligomers or polymers having polysulfone as the main chain and aliphatic hydroxyl groups at the ends can be prepared by reacting bisphenol A and 4,4'-dichlorodiphenylsulfone in a solvent such as dimethyl sulfoxide in the presence of potassium carbonate. Alternatively, an oligomer or polymer having aromatic hydroxyl group terminals is obtained by reacting a high molecular weight polysulfone with caustic soda in a solvent such as dimethyl sulfoxide, and then reacting this with epichlorohydrin or the like in the presence of an alkali. can be obtained by

Furthermore, oligomers or polymers having polyetherimide as the main chain and amino groups at the ends can be easily obtained, for example, by reacting high molecular weight polyetherimide with a diamino compound.

In the present invention, it is sufficient that some of the terminal groups are hydroxyl groups and/or amino groups, preferably 50% or more of all terminal groups are hydroxyl groups and/or amino groups. The flow temperature of the oligomer or polymer is preferably 300°C or lower, especially 2
The temperature is preferably 80°C or lower.

[0014] Further, the degree of polymerization of the oligomer or polymer may be about 0.05 to 0.5 in terms of intrinsic viscosity;
More preferably, it is 0.1 to 0.4.

In the present invention, a monomer having two hydroxyl groups and/or amino groups, preferably an aliphatic hydroxyl group and/or an aliphatic amino group in the molecule, such as a compound having 2 to 20 carbon atoms, is used as the viscosity modifier. It is also possible to incorporate it as a part of the above oligomer or polymer, for example, up to 30% by weight. Examples of such compounds include compounds having a hydroxyl group, such as aliphatic diols such as hexamethylene diol, dodecamethylene diol, diethylene glycol, and triethylene glycol, and alicyclic groups such as cyclohexane dimethylol and tricyclodecane dimethylol. aliphatic diol, 1
, 4-bis(β-hydroxyethoxy)benzene, 2,
Aliphatic compounds containing aromatic groups such as 2-bis(β-hydroxyethoxyphenyl)propane, 1,1-bis(β-hydroxyethoxyphenyl)cyclohexane, bis(β-hydroxyethoxyphenyl)sulfone, xylylene glycol, etc. Examples include diols and the like. In addition, examples of compounds having an amino group include aliphatic diamino compounds such as hexamethylene diamine and dodecamethylene diamine; aliphatic diamino compounds having an alicyclic group such as 1,4-diaminocyclohexane and 1,2-diaminocyclohexane; Diamino compounds having an aromatic group such as xylylene diamine, m- or p-phenylene diamine, 4,
4'-diaminodiphenylmethane, 3,4'- or 4,4'-diaminodiphenyl ether, 4,4'
- Aromatic diamino compounds such as diaminodiphenylsulfone can be exemplified.

[0016] Examples of compounds having a hydroxyl group and an amino group include ethanolamine and the like.

Furthermore, in the present invention, a polyol compound having three or more hydroxyl groups, or a polyol compound having three or more amino groups,
A small proportion of a polyamine compound having at least 5% by weight, for example, 5% by weight.
It can also be used below.

Next, the biscyclic iminoester used in the present invention has the following formula (I).

[0019]

[Chemical formula 1] (In the formula, Q and R are a direct bond or a divalent organic group. ) is a compound represented by

The divalent organic group represented by Q in the above formula (I) is, for example, an aromatic group having 6 to 16 carbon atoms, or an aromatic group having 2 to 10 carbon atoms.
Preferred examples include aliphatic groups having 6 to 12 carbon atoms, and more specifically m-phenylene, p-phenylene, tolylene, diphenylene, 1,5-naphthylene, 2
, 6-naphthylene, 2,7-naphthylene,

[0021]

[Formula 2] (wherein, X is -CH2-, -O-, -S-, -SO2
-, -CO-, -OCH2 CH2 O-, etc. ),

[0022]

embedded image (wherein, X' is -CH3, NO2, halogen, phenyl, etc.), -(CH2)n - (wherein, n is a number from 2 to 10), 1,4- Preferred examples include cyclohexylene.

In addition, the divalent organic group for R in the above formula (I) includes an aromatic group having 6 to 16 carbon atoms, and an aromatic group having 1 to 10 carbon atoms.
Preferred examples include aliphatic groups and alicyclic groups having 6 to 12 carbon atoms, and more specific examples include o-phenylene, methylene, ethylidene, isopropylidene, and 1,1-cyclohexylene. -Phenylene and isopropylidene are preferred.

These biscyclic iminoesters include 2,2'-bis(4,4'-dimethyl-5-
oxazolone), 2,2'-tetramethylenebis(4
, 4'-dimethyl-5-oxazolone), 2,2'-
m- or p-phenylenebis(5-oxazolone), 2
,2'-m- or p-phenylenebis(4-methyl-
5-oxazolone), 2,2'-m- or p-phenylenebis(4,4'-dimethyl-5-oxazolone)
, 2,2'-tetramethylenebis(4H-3,1-benzoxazin-4-one), 2,2'-m- or p-
Phenylenebis(4H-3,1-benzoxazine-4-
On) etc. are exemplified.

The proportion of the bicyclic imino ester to be used is determined based on the total amount of hydroxyl groups and the total amino group of the oligomer or polymer having a hydroxyl group end and/or amino end, and the monomer which may be used in combination in a small proportion depending on the case. It is particularly preferable that the amount and the amount of cyclic imino ester groups are substantially equivalent, but any one of the components may be in excess of about 10 to 20%.

In the present invention, the above-mentioned aromatic polyether oligomer or polymer having a hydroxyl group terminal and/or an amino group terminal is heated to react with a bicyclic imino ester. °C, more preferably 150-33
It is preferable to carry out the reaction at a temperature of 0° C., particularly preferably from 200 to 310° C., under normal pressure to pressurization, for example in an inert gas atmosphere such as nitrogen gas. The reaction time is preferably 30 seconds to
It is about 30 minutes, more preferably about 1 to 20 minutes.

[0027] In the present invention, it is preferable to use a catalyst in the above heating reaction. Examples of catalysts include metals such as sodium, potassium, lithium, calcium, magnesium, titanium, tin, zinc, antimony, germanium, and tungsten, and compounds thereof such as hydrides, hydroxides, alkoxides, and oxides. Can be done.

More specifically, a normal anionic polymerization catalyst,
Examples include those commonly used as cationic polymerization catalysts, coordination anionic polymerization catalysts, transesterification catalysts, and the like. Specifically, alkyllithium such as n-butyllithium, Lewis acid such as ferric chloride, aluminum chloride,
Preferred examples include various Grignard compounds such as ethylmagnesium bromide and ε-caprolactammagnesium bromide, trialkyl aluminums such as triethylaluminum, and metal alkoxides such as tributoxyaluminum and tetrabutoxytitanium. Among these, coordination anionic polymerization catalysts are particularly preferred.

[0029] Naturally, this also includes those which are normally known as cationic polymerization catalysts, such as aluminum chloride, but which can be converted into a coordinating anion type within the reaction system. Examples of such preferable catalysts include metal alkoxides such as tetraalkoxytitanium and trialkoxyaluminum, alkyl metals such as triethylaluminum, and Lewis acids such as aluminum chloride. Among these, titanium tetraalkoxides such as titanium tetrabutoxide and titanium tetraisopropoxide, and trialkylaluminums such as triethylaluminum are particularly preferred.

The amount of the catalyst used is about 0.001 mol% to 1 mol%, preferably 0.005 mol% to 0.5 mol%, based on bisacylcaprolactam.
Particularly preferred is 0.01 to 0.1 mol%.

The method of the present invention can be applied to reaction molding; for example, both starting materials and, in some cases, other types of plastic polymers, fillers, stabilizers, and other additives are charged into a mold that has been heated to a predetermined temperature, and the mold is heated and held. By doing so, a resin molded article having a desired shape can be obtained.

The method of the present invention is particularly effective in producing composite materials by carrying out a heating reaction in a reinforcing matrix such as carbon fibers, glass fibers, and the like. Reinforcement matrix is short fiber aggregate, nonwoven fabric,
It means a structure formed from long fiber woven fabric, knitted fabric, etc.

In the present invention, the final polymer has an intrinsic viscosity of 0.4 or higher, preferably 0.1 or higher than that of the initial oligomer or polymer, and particularly preferably 0.1 or higher.
It is desirable that the number is 2 or more.

[0034]

[Effect of the invention] By using the production method of the present invention,
By using raw materials with relatively low viscosity, it is possible to obtain a substantially linear resin with excellent thermal and mechanical properties in a very short time.

[0035]

[Examples] The present invention will be further explained below with reference to Examples. In addition, all "parts" in the examples mean "parts by weight", and the intrinsic viscosity was measured at a temperature of 35° C. using a mixed solution of phenol and tetrachloroethane 60:40 (weight ratio). In addition, the secondary transition point (Tg) was determined by DSC at a heating rate of 2.
Measured at 0°C/min.

[0036]

[Example 1] In a three-necked flask equipped with a stirrer and a Dean-Stark tube, 760 parts of dimethyl sulfoxide, 302 parts of toluene, 103 parts of 2,2-bis(4-hydroxyphenyl)propane (bis-phenol A), 4,4'
-100 parts of dichlorodiphenyl sulfone and 116 parts of anhydrous potassium carbonate were charged. Mixture 130-14
It was kept at 5° C. for 4 hours and the water was continuously removed by azeotrope with toluene. After cooling, salts, solvents and impurities were removed using a large amount of water and methanol, and the polymer was dried.

A three-neck flask equipped with a stirrer was charged with 186 parts of the polymer synthesized by the method described above, 100 parts of epichlorohydrin, 172 parts of anhydrous potassium carbonate, and 874 parts of dimethyl sulfoxide.

Heat the mixture to 90-105°C for 6 hours while stirring.
Saved time. After cooling, salts, solvents, and impurities were removed with a large amount of water and methanol, and the mixture was dried at 80° C. under vacuum.

The intrinsic viscosity of the obtained polysulfone oligomer having hydroxyl group terminals was 0.31. 100 parts of the polysulfone oligomer obtained by the method described above and 0.1 part of titanium tetrabutoxide were placed in a three-necked flask equipped with a stirrer, and after purging with nitrogen,
The mixture was heated and melted at ℃. To this, 2,2'-bis(4
1.5 parts of H-3,1-benzoxazin-4-one) was added, and the mixture was stirred at 280°C for 10 minutes. The obtained product had an intrinsic viscosity of 0.50 and a Tg of 184°C.

[0040]

[Example 2] 100 parts of polysulfone oligomer synthesized by the method described in Example 1, 0.1 part of titanium tetrabutoxide, 2,2'-p-phenylenebis(4,
1.5 parts of 4'-dimethyl-5-oxazolone) was heated to 240° C. and reacted by the method described in Example 1.

The intrinsic viscosity of the obtained product is 0.41, T
g was 186°C.

[0042]

[Example 3] In a three-necked flask equipped with a stirrer, 100 parts of polyether sulfone (manufactured by Union Carbide Co., trade name: Udel), 1100 parts of dimethyl sulfoxide, and 10 parts of hexamethylene diamine were charged, and heated to 170°C.
Stirring was performed for 30 minutes. After cooling the mixture, it was reprecipitated with methanol, washed, and dried at 100° C. for 5 hours. The yield of the resulting polysulfone oligomer having an amino group at the terminal was 96 parts, and the intrinsic viscosity was 0.30.

100 parts of the polysulfone oligomer obtained by the method described above and 1.7 parts of 2,2'-p-phenylenebis(4,4'-dimethyl-5-oxazolone) were placed in a three-necked flask equipped with a stirrer. After charging and purging with nitrogen, the mixture was heated to 240°C and stirred for 10 minutes. The obtained product had an intrinsic viscosity of 0.44 and a Tg of 177°C.

[0044]

[Example 4] 2,2
1.5 parts of -bis(4H-3,1-benzoxazin-4-one) and 0.1 part of titanium tetrabutoxide were uniformly blended, and the mixture was applied to a polycarbonate film.
The carbon long fiber plain woven fabric, the blend, and the polycarbonate were laminated in this order and press-molded for 10 minutes at 280° C. and 20 kg/cm 2 . The polymer was uniformly impregnated into the long carbon fiber plain weave, resulting in a strong laminate.

100 parts of polyetherimide (manufactured by GE, trademark: Ultem), 880 parts of dimethyl sulfoxide, and 6.9 parts of m-xylylenediamine were added to a three-necked flask equipped with a stirrer, and the mixture was melted at 170°C for 10 minutes. Stirring was performed. After cooling the mixture, it was reprecipitated with methanol, washed, and then dried at 100° C. for 10 hours.

The yield of the polyetherimide oligomer having amino groups at the terminals was 96 parts, and the intrinsic viscosity was 0.
It was 29.

Polyetherimide oligomer 1 obtained by the method described above was placed in a three-necked flask equipped with a stirrer.
00 parts, 2,2'-p-phenylenebis(4,4'
-Dimethyl-5-oxazolone) was added, the atmosphere was replaced with nitrogen, and the mixture was heated to 240°C and stirred for 10 minutes. The obtained product has an intrinsic viscosity of 0.41 and a Tg of 171°C.
Met.

Claims (1)

[Claims] [Claim 1] A substantially linear aromatic polyether oligomer or polymer having a hydroxyl group end and/or an amino group end and a biscyclic imino ester are subjected to a heating reaction. Thermoplastic resin manufacturing method.