JPS58180506A - Continuous modification of resin - Google Patents

Abstract

PURPOSE:To carry out the continuous production of an imidecontaining resin having a good color and excellent heat resistance, by adding an amine to a specified resin composition molten by heating in an inert gas atmosphere and then removing water and an excessive amine. CONSTITUTION:A resin composition prepared by adding 0-30pts.wt. rubber, butadiene content >=70wt%, to 100pts.wt. copolymer comprising 2-50wt% maleic anhydride, 50-98wt% aromatic vinyl compound and 0-48wt% at least one different unsaturated compound is fed from a feed inlet 3 into an extruder to which a sufficient quantity of an inert gas is supplied and molten by heating at 150- 250 deg.C. Then, an amine in an amount at least equivalent to that of maleic anhydride is added from a storage tank 5 through a feed inlet 4. Then, this mixture is held within a conducit 6 for 5-30min and led to an extruder II evacuated by a vacuum pump 9 through vents 7 and 8 and water and an excess amine are passed via a heat-exchanger 10 and recovered in a tank 11, and an imide-containing resin composition is discharged through a nozzle 12.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an imide derivative-containing copolymer or a composition containing the copolymer.

Copolymers of aromatic vinyl compounds and maleimides or N11l-converted maleimides have high heat resistance and are therefore important resins for light electrical parts and automobile interior materials. On the other hand, the maleimide copolymer has good compatibility in blending with various other resins, and its uses are becoming increasingly widespread.

However, the method for producing such a very useful maleimide co-conjugate has many problems and has not been developed on an industrial scale. For example, the most common method for producing the copolymer is the mutual direct copolymerization of an aromatic vinyl compound 5, such as styrene, maleimide or N-phenylmaleimide, which has been known for a long time. However, like maleic anhydride, these maleimide monocasings tend to form an alternating straight polymer of 1/:/ for aromatic vinyl compounds, and at the same time the molecular weight of the resulting copolymer is low, resulting in poor mechanical strength. It is unsatisfactory in this respect. This is a method for obtaining a copolymer with a uniform composition using non-equimolar copolymers.

Tokukai Akira Ogu? As described in Publication No. 3θ9/, it is common to gradually incorporate an imide compound as an aromatic vinyl compound such as styrene is polymerized. The various techniques involved in these polymerization methods are strikingly similar to those for maleic anhydride. The biggest difference is that maleic anhydride is readily available as an inexpensive chemical, whereas maleimides are not commercially available as general products. Many methods have been proposed for the synthesis of various N[converted maleimides as maleic anhydride raw materials, but none of them are simple to operate, have high raw material costs, and have low reaction yields. It's not that expensive either. For this reason, despite many studies being conducted, various N1-converted maleimi F monopolymers have not been produced on an industrial scale.
l& has not yet been sold.

Therefore, it has become easier and more common to first obtain a copolymer of an aromatic vinyl compound and maleic anhydride and then modify it into a copolymer containing an imide derivative.

For example, Japanese Patent Publication No. 6-39467 and U.S. Patent @3
．． No. 91,907 discloses that styrene/maleimide and styrene/ N-
A method is disclosed that outperforms substituted maleimide conjugation.

However, in this method, the granular copolymer after the reaction contains multi-wrinkled amines and water, so it cannot be used as a resin raw material for products as it is, and 4iI with a degassing device is used.
Volatiles must be removed with cIi. Furthermore, this modification method is a patch method, which is not necessarily advantageous in terms of industrialization. Ammonia and amines are dissolved in the suspended water, and there is a lot of odor when handling it.

Although maleimide and NW1-converted mashimaleimide coelectronic composites are expected to be used in a wide range of applications, they have not been produced on an industrial scale due to the complicated manufacturing method.

In view of the above, as a result of intensive research, the present inventors have found an industrially advantageous method for obtaining a high-quality imide-containing composition with a good color tone and even higher heat resistance.

First, the present invention is directed to an aromatic vinyl compound containing maleic anhydride! 0-? Copolymer 1 consisting of /wt-1 and other 7 or more unsaturated compounds o-tiei
When modifying a resin composition containing 0 to 30 parts by weight of a rubber in which 70 parts by weight or more are butadiene based on 0 parts by weight, into a resin composition containing an imide, first, the resin composition is After heating and melting the resin composition and adding at least an equivalent amount of amines to the amount of maleic anhydride,
The present invention relates to a continuous modification method characterized by maintaining this state for 5 to 30 minutes, and then removing water and excess amines under reduced pressure.

A third feature of the invention is a non-aqueous one-step continuous manufacturing process, which significantly reduces manufacturing costs. The characteristic of @λ is a chemical reaction in the molten state, but /6O-20O℃
Even if the reaction is completed at a relatively low temperature and in a short time of ~30 minutes, the imidization yield is high and a resin with little discoloration can be obtained.

The third feature is that when the water produced as a result of the imidization reaction is removed by evaporation in the vacuum degassing section, it serves to promote the removal of residual amines and residual copolymer residue. As a result, a high-quality modified product with further improved heat resistance can be obtained by significantly reducing residual materials. The feature of m4t is that the added amines are added in an equivalent or excess weight to the anhydrous maleic*ii bound in the starting resin, but the excess amines are completely recovered in the vacuum degassing section, and after water is separated. It can be reused as is. The amount of raw material loss is surprisingly small. @j's unique feature is that it uses raw materials that can be obtained at low prices. Commercially available maleic anhydride-containing resins as starting materials can be used as they are, and other Type I copolymers can be produced by known methods. As described above, the simple and cost-effective manufacturing method makes it possible to supply a high-quality resin with a wide range of uses.

The present invention will be explained in detail below.

The aromatic vinyl compounds in the copolymer used in the present invention include styrene, α-methylstyrene, vinyltoluene, ethylstyrene, isobutylamine, turn-Y-1
Styrenes such as chlorostyrene, chlorostyrene, and dichlorostyrene are the most common. That is, styrene
Maleic anhydride copolymers are basic. In this case, maleic anhydride is 2~! Preferably, the weight of the styrene is 30-9. If the weight of maleic anhydride is less than 100 g, high heat resistance cannot be expected even if imidization is performed. If the anhydrous malemono content exceeds 10% by weight, a high temperature is required for melting, making it impossible to obtain an imidized product with good color tone.

Furthermore, a multicomponent copolymer containing seven or more unsaturated compounds may be used. Styrene-maleic anhydride copolymer is a resin with high heat resistance, and when modified into an imide, the heat resistance becomes even higher, but mechanical strength and chemical resistance may be unsatisfactory.

To improve this point, acrylonitrile and methacrylotrile. A multicomponent copolymer into which an unsaturated compound such as methyl methacrylate is introduced is used. Styrene-maleic anhydride-acrylonitrile terpolymer, styrene-maleic anhydride-methyl methacrylate terpolymer, styrene-maleic anhydride-methacrylonitrile terpolymer,
Styrene-maleic anhydride-acrylonitrile-methyl methacrylate quaternary copolymer, styrene-maleic anhydride-acrylonitrile-methacrylonitrile-methyl methacrylate quinary copolymer, etc. all have excellent mechanical strength and chemical resistance. It is a heat-resistant resin, and is modified into an imide-containing side fat with further improved heat resistance by the method of the present invention.

Generally, when maleic anhydride and acrylonitrile or methachloronitrile are left at high temperatures, a mutual reaction occurs and a crosslinked product is formed, resulting in a decrease in fluidity, but the method of the present invention has extremely high thermal stability. It changes into a good resin.

As the amines used to impart benign properties to the imide, primary amines and their aqueous solutions, including ammonia gas and aqueous ammonia, can be used. For example, methylamine, triamine, normal propylamine, isopropylamine, butylamine, isobutylamine, secondary butylamine, pentylamine, isopentylamine, 7.2-
These include dimethylpropylamine, 5-hexylamine, cyclohexylamine, octylamine, and stearylamine. Alkoxyalkylamines such as λ-methoxyethylamine and 3-methoxypropylamine can also be used. Aromatic amines include aniline, ortho-toluidine, 2. y,, t-trichloroaniline, 5-gunitrochloridine, alpha naphthylamine, beta naphthylamine, 2-methoxyaniline,
These include dermethoxyaniline, low ethoxyaniline, y-ethoxyaniline, and the like. Allylamine, benzylamine, D- and L-alphafebenthylamine.

Imidized products such as beta-phenethylamine can also be effectively produced by the method of the present invention. Polyamines such as diethylaminoethylamine and hydroxylamines such as impropaturamine can also be used.

As a means for increasing the malt impact resistance of a heat-resistant resin, there is a method in which the above-mentioned maleic anhydride-containing copolymer is used as a matrix part and rubber mainly composed of butadiene is dispersed as spherical bodies having a diameter of 0.7 to 10 microns. is common. In order for these rubber spheres to exhibit the impact resistance effect, compatibility with the matrix part is an essential condition, and for this reason, the surface of the rubber spheres in the dispersed phase has compatibility with the matrix part. Grafting the copolymer. By modifying the resin composition thus obtained into an imide-containing material by the method of the present invention, it retains double impact resistance and further improves heat resistance and thermal stability. In this case, the rubber used for the purpose of increasing impact resistance is preferably a polymer containing polybutadiene, hesisbobutadiene, or butadiene polymerized with an alkyllithium catalyst in an amount of 70 or more times. In rubbers in which butadiene is copolymerized with styrene, acrylonitrile, etc., if the butadiene content is less than 70% by weight, the impact properties of the raw material and the imide-modified resin product are significantly reduced.

Such rubber is preferably used in an amount of 30 parts by weight or less based on 10θ parts by weight of the heat-resistant copolymer in the matrix portion. When the amount exceeds 30 parts by weight, the flexural modulus of the resin decreases, resulting in a decrease in practical heat resistance.

In the resin modification method of the present invention, various means such as a mixing roll, a Flabender, a Banbury mixer, and a single-screw or co-screw type extruder can be used to heat-melt the resin and mix it with amines. Although combinations can be used, the method using an extruder is the most common process.

First, when heating and melting the maleic anhydride-containing copolymer and resin composition, which are modified raw materials, it is important to supply sufficient nitrogen gas or inert gas and remove as much oxygen as possible to remove imidized materials with a small degree of discoloration. It is necessary to obtain E. It is desirable to remove oxygen from the amines added as much as possible.

If the amount of amines added is equal to the amount of maleic anhydride, the imidization rate will be unsatisfactory. Usually 2 to 3 times the molar amount is added. If amines from large sea bream are further added, the imidization yield will further improve.

The color tone of the produced imide compound becomes worse.

The temperature of the heated molten resin mixed with the added amines is generally above 730°C and below 2J-0°C.
-200°C is particularly preferred. The imidization reaction progresses faster at higher temperatures, but the degree of discoloration is also greater.

If the temperature is below 760°C, the melt viscosity of the resin will increase considerably, and crosstalk with amines will become insufficient.

After the molten resin and amines are kneaded, the time for which they are kept in that state is related to the yield of the imidization reaction. The longer the holding time is, the higher the yield of the imidization reaction will be. However, since most of the objectives are achieved by imidizing maleic anhydride in an amount of substantially more than 10 mol, the holding time is 5
~30 minutes is best. If it is longer than 30 minutes, the degree of discoloration of the imidized product will be large, and if it is shorter than 5 minutes, the imidization reaction yield will be insufficient.

After the imidization reaction is completed, it is necessary to remove water, unreacted amines, and residual amounts of zimmers present in the resin using as high a vacuum as possible. The greater the amount of the above-mentioned substance remaining, the greater the degree of discoloration of the produced imidide. The vacuum degree of the vacuum chamber is preferably 30 Torr or less.

EXAMPLES Below, in order to further clarify the present invention, examples will be given and explained, but the scope of the present invention is not limited by the examples.

First, a resin mainly composed of one type of styrene-maleic anhydride was prepared as a starting material resin to be imidized and modified. Raw material resins A, B, and C are Dylark 232 and Disheek 332, respectively, commercially available from ARCO. Dailark 3! θ.

Manufacturing method of raw resin resin: 75 weights of styrene, 11813 weights of anhydrous malein,
Prepare 100 blood wrinkles with a mixture of 10 parts by weight of acrylonitrile. 20 parts of methyl ethyl ketone, / parts by weight of tertiary dodecyl mercaptan, /, /-bis(
tert-butylperoxy) -3,3,J -)
A mixture of 0 and Oj parts by weight of remethylcyclohexane is prepared and first continuously fed to the first stage reactor at a rate of /, OLy/H.

This first stage reactor has an internal volume of 2. This is a completely mixed type of jt. The polymerization temperature was 120°C. The polymerization liquid coming out of the first stage reactor contains a solid content of ginseng/Eriyu, and is immediately and continuously supplied to the second stage reactor. The second stage reactor has an internal volume of 1. /D=j layer tILfJ. The polymerization temperature is 130°C in the upper row.
The temperature at the bottom was 7.0°C. The polymerization reaction liquid is continuously spewed out, but when a part of it is extracted, the solid content is 50% by weight.
Met.

Therefore, the polymerization conversion rate is 63 wt. The continuously taken out polymerization reaction solution was immediately heated to 210°C, ljmI) 1g1
After the unreacted monomers and solvent are separated, it is discharged from the bottom of the vacuum chamber using a screw type extruder. The resulting copolymer is styrene-anhydrous! The line indicates that it is a ternary copolymer of leic acid and acryltetranitrile. Details are shown in Table-7.

Preparation of Raw Material Resin E: An AB8 resin rubber concentrate having a rubber content of 60% by weight is prepared by emulsion polymerization using polybutadiene latex in a known manner. -The detailed composition is styrene 7θ heavy,
30% by weight of acrylonitrile. This AB8 rubber concentrate 30% weight and the previously produced raw material resin D (
70 weight of styrene-maleic anhydride-acrylonitrile terpolymer was kneaded using a coaxial extruder. The resultant product is a styrene-maleic anhydride-acrylonitrile copolymer, which is known as raw plum fat E. The details are summarized in the table.

In Table-/, the maleic anhydride content was determined by neutralization titration.
Acrylo and nitrile contents were determined using an infrared spectrophotometric needle. The rubber content in raw materials C and E was determined using an infrared spectrophotometer needle and pyrolysis gas chromatography.

Figure '1Il1 is an example of the flow of an apparatus for carrying out the continuous modification method of resins according to the present invention. Summer is the first extruder, and 3 is its raw material arm supply port. i enough for 3
1 bulk gas is supplied. Hiro is a supply port for amines,
Amines are supplied by a pump from j. B is a conduit consisting of double pipes that can be freely changed in length and pipe size and kept at the required temperature.

(2) is the second extruder, 7.1 is its vent hole, and the pressure is reduced by a vacuum bomber. Bentrore! The more separated amines and water are condensed in the heat exchanger IO and recovered in the tank //. The produced resin is continuously obtained from the nozzle port lλ of the second extruder (2).

Examples are shown below. (Hereinafter, blank space) Example 1 Using a single-screw extruder shown in 11/IIK, raw resin was supplied at a rate of 0/H.

λ, liolto toluidine! , and was fed at a rate of P/H. The temperature of the molten polymer at the exit of the first extruder is 191℃
Met. Conduit 1 was a double tube with an inner tube of 2 inches (outer diameter reference) and an outer tube 3 inches (outer diameter reference), and was heated with heated oil at 200°C. The length of conduit B was such that the average residence time of lI#s polymer was lj minutes. #! For two extrusions 1 and 11, a twin screw extruder with ≠j- is used, and the vent lower is /jT・r.
r, ventro t was depressurized to J T@rr. Nozzle 12
The obtained molten jM11m was cooled into a strand shape and made into a pellet shape using a cutter.

The ortho-toluidine separated from the resulting resin Mo-7 was collected in a drum, and after the moisture content I11, it was again used as a solution. The amount of imidized product was determined to be 3 mol by using an infrared spectrometer. Other physical properties are listed in Table-2.

Example - Aniline 9 was substituted for ortho-toluidine in Example 7.
．． It is the same as Example -/, except that it was supplied at a rate of ≦1. The imidization yield of the resulting resin A-2 was determined to be 0 mol as determined by an infrared spectrophotometric needle. Other physical properties are shown in Table C.

Example-3 Example-3 except that cyclohexylamine was supplied at a rate of ¥JK/H in place of ortho-toluidine in Example-/.
/ is the same as The resulting imidization yield of resin-3! I was very disappointed. Other physical properties are shown in Table C.

Example - In place of the raw material person in Example -/, raw material B was supplied at a rate of θi. On the other hand, ortho-toluidine was supplied to No. 6 and No. 6 at a rate of 4/H. Other conditions are the same as in Example-/. The imidization yield of the resulting resin B-/ was 3 moles of ♂g. Other physical properties are shown in Table C.

Example-j Instead of raw material A in Example-7, raw material C was supplied at a rate of 2θ/H. On the other hand, aniline was fed as an amine at a rate of 0. Other conditions are the same as in Example-/. What is the imidization yield of the obtained resin C-/? There were 33 moles of tatami. Other physical properties are shown in Table C.

Example-≦ Example-/Instead of the raw material person, the raw material amount is increased to 20+! /1'
(on the other hand, aniline as an amine at a rate of 9./Kv/
It was fed at a rate of H. Other conditions are the same as in Example-/. The imidization yield of the resulting resin D-/ was 900 moles. Other physical properties are listed in Table-2.

Example 7 A thermal stability test was conducted using the raw material resin and the resin D-/No. 29 obtained in Example 6. 260% of the above resin
℃, / (> Torr vacuum heating furnace. Then, 7
Samples were removed from the vacuum heating furnace every hour and heated to 23θ℃.
, 3. Melt flow index (M
FI) was measured. The results are shown in Table-3.

Example - Instead of raw material A in Example -/, raw material resin E was replaced with 20 and 4Z/
) (on the other hand, aniline was fed as an amine at a rate of 6.jl.Other conditions were the same as in Example-/.The imidization yield of the resulting resin 18-/ was 911 mol/cm). 3. Other physical properties are listed in Table C.

As shown in the Examples in Table 2, the imidized modified resin obtained by the industrial method of the present invention maintains good color tone and has a higher heat resistance temperature.

Further, from the Examples shown in Table 3, the obtained imidized modified side fat has improved thermal stability.

The measurement of Vicat softening temperature in Table 2 is 8TMD-/,
Based on 3-26. The color tone is based on observations of injection molded test pieces.

(Left below) MFI after retention in vacuum heating furnace at 26θ℃ and /θTorr
value

[Brief explanation of drawings]

Figure 7 shows seven examples of the flow of an apparatus for implementing the continuous modification method of resin based on the present invention.Patent applicant: Toru Hoshino, Patent Attorney, Asahi Dow Co., Ltd.

Claims (2)

[Claims] (1) Maleic anhydride-~! θ weight −1 aromatic vinyl compound 30 −? A resin composition containing 0 to 30 parts by weight of a rubber in which 70 parts by weight or more of S is butadiene, based on 10 parts by weight of a copolymer consisting of 7 or more unsaturated compounds θ to 4tt by weight When modifying a substance into a resin composition containing an imide, first heat and melt the resin composition in a nitrogen gas or inert gas atmosphere, add amines in an amount equivalent to or more based on the amount of maleic anhydride, That state! A continuous modification process characterized by holding for ~30 minutes, followed by removal of water and excess amines under reduced pressure. (2) The method according to claim 1, wherein the other/or more unsaturated compounds are acrylonitrile, methachloronitrile, methyl methacrylate, or a combination thereof.