JPH02178310A - Methacrylimide-containing polymer and resin composition containing the same - Google Patents

Abstract

PURPOSE:To obtain the subject polymer, having structural units derived from methacrylimide ring structural units and structural units derived from an ethylenic monomer in a specific proportion with respective specified values or below of iron content and distribution width of imidation ratio and excellent in transparency and heat coloring properties with time. CONSTITUTION:For example, a methacrylic acid ester, such as methyl methacrylate, alone or a mixture thereof with an ethylenic monomer, such as styrene, copolymerizable with the above-mentioned ester is mixed with an inert solvent, such as benzene, a radical polymerization initiator, such as di-tert- butyl peroxide, and a polymer molecular weight modifier, such as n-butyl mercaptan, and polymerization reaction is carried out. The resultant polymer is then imidated with an imidating substance (e.g. methylamine) expressed by formula I (R is H, 1-20C aliphatic hydrocarbon group, etc.) to afford the objective polymer, consisting of 2-100wt.% methacrylimide ring structural units expressed by formula II and 0-98wt.% structural units derived from the ethylenic monomer and having <=20ppm iron content and <=5wt.% distribution width of imidation ratio.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a methacrylimide-containing polymer with excellent heat resistance, transparency, and colorability over time when heated, and a polymer containing this methacrylimide-containing polymer that has good colorability over time when heated. The present invention relates to a resin composition that has excellent properties.

[Prior Art] Methyl methacrylate polymer is not only transparent but also has excellent weather resistance and mechanical properties, so it is used as a high-performance plastic optical material and decorative material.In recent years, it has been used for short-distance optical communications, optical sensors, etc. Application development is progressing in the field. However, the heat distortion temperature of methyl methacrylate polymer is as low as after mil, making it unsuitable for use in fields requiring heat resistance, and there is a strong demand for improved heat resistance.

A method of imidizing a methyl methacrylate polymer is known as a method for improving the heat resistance of the methyl methacrylate polymer. and primary amines,
A method of reacting ammonia or a primary amine or a compound that generates ammonia by heating in the presence of a solvent (U.S. Pat. No. 2,146,209, German Patent No. 1,077,872 and German Patent No. 1, 242.369), (2) a method of reacting a methyl methacrylate polymer with a primary amine in the presence of water (U.S. Pat. No. 3.284.
No. 425) and (3) a method of reacting an acrylic polymer with ammonia or a primary amine in an extruder (1).
U.S. Special Forces 21 No. 4,246.374) has been proposed.

However, in the method (I), it is difficult to completely separate the solvent from the imidized polymer produced on a commercial scale due to the high boiling point of the solvent used, and as a result, The resulting imidized polymer becomes colored and the transparency of the resulting polymer decreases.

In addition, in the method (2) above, the polymer to be partially imidized is j: ↑ in order to react in the presence of water.
Hydrolysis of the methyl methacrylate segment occurs at R'6, making it difficult to obtain a monomer polymer having the desired heat resistance, and also making it difficult to carry out a uniform imidization reaction. Furthermore, in the method (3) above, it is difficult to carry out a uniform imidization reaction because the imidization reaction is a reaction between a highly viscous polymer and a gaseous imidization substance. (Imidized) 1 coalescence was obtained.

Therefore, although the heat resistance of the garbage monopolymer obtained by the method described in 1-1 is excellent, if it is attempted to be commercially produced, it may have poor transparency, a substantial decrease in molecular weight, or Currently, these methods have not yet been put into practical use because imidization is non-uniform.

In addition, resin compositions obtained by mixing and blending the methacrylimide-containing polymer with other types of thermoplastic polymers may cause the molded product itself to have a strong yellowish color, or the molded product may change over time due to heating. The current situation is that the yellowing color is increasing and the commercial value is significantly decreasing.

[Problems to be Solved by the Invention] The purpose of the present invention is to improve the drawbacks of the prior art as described above, and to improve the excellent optical properties inherent to methacrylic acid ester polymers.
In addition to providing a methacrylimide-containing polymer that maintains properties such as properties, mechanical properties, weather resistance, and molding processability, and has excellent transparency and heat resistance, it also provides a polymer that can be used with such polymers and other types of thermoplastic polymers. An object of the present invention is to provide a methacrylimide-containing polymer resin composition which is composed of a methacrylimide-containing polymer resin composition and has less yellowish color.

[Means to solve the problem]

The above-mentioned object is to provide the methacrylimide-containing polymer of the present invention,
That is, the formula (I) (wherein R is a hydrogen atom or an aliphatic group having 1 to 20 carbon atoms,
A thermal 11J plastic nail coalescence consisting of 2 to 100 weight percent of structural units represented by aromatic or alicyclic hydrocarbon groups (representing aromatic or alicyclic hydrocarbon groups) and 0 to 98 weight percent of structural units derived from ethylenic monomers, which is a small coalescence. The iron content inside is 20. This can be achieved by using a methacrylimide-containing polymer having a molecular weight of 5% or less and an imidization rate distribution +l+ of 5% or less in the polymer.

Furthermore, the present invention provides the above methacrylimide-containing polymer 1
Copolymers (A
BS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), methacrylic resin polymer containing methyl methacrylate as a main component, thermoplastic polyester, modified and/or main modified polyolefin, polyamide resin, polyphenylene A resin composition comprising 99 to 1% by weight of a thermoplastic resin selected from oxides and polycarbonates is provided.

The methacrylimide-containing polymer of the present invention, which has an iron content of 20 ppm or less and an imidization rate distribution width of 5% or less, has a methacrylic acid ester polymer and a general formula (II) R-NH, (II) (formula where R is a hydrogen atom or an aliphatic group having 1 to 20 carbon atoms;
or aromatic or alicyclic hydrocarbon group) (hereinafter abbreviated as "imidized substance") by a specific method, and then It can be produced by a method in which volatiles are removed from a reaction solution obtained by imidization reaction in the presence of a solvent and extrusion shaping is carried out under specific conditions. This method may be either batchwise or continuous.

More preferably, the methacrylimide-containing polymer of the present invention can be produced industrially and continuously by the following method.

That is, in continuously producing a methacrylimide-containing polymer, 10 to 60% by weight of an inert solvent, 90 to 60% by weight of an inert solvent,
40% by weight of a methacrylic ester or a mixture of a methacrylic ester and a copolymerizable ethylenic monomer;
0.0001-0.5% by weight of radical initiator, 0-5
A solution consisting of 8% by weight polymer molecular weight modifier is introduced continuously into the substantially uniformly mixed first reaction zone, followed by 8% by weight in the second reaction zone with plug flow flow.
80 of at least the initial monomer at a temperature of 0 to 170°C.
After converting the compound into a polymer, the polymerization reaction solution and the imidized substance represented by formula (II) above were heated at 50 to 190°.
The imidization reaction is carried out at a temperature of 150 to 350 °C in a third multi-stage reaction zone having at least two zones by substantially uniform mixing for at least one minute at a temperature of 150 to 350 °C. The reaction solution heated to a temperature of 350°C is introduced into a temperature range below atmospheric pressure, and after continuously separating and removing volatile substances by flashing, the flushed polymer is continuously received by a specific screw and treated with a specific Shape using an extruder.

Hereinafter, the methacrylimide-containing polymer of the present invention, a resin composition containing the same, and a method for producing the same will be explained in detail.

The methacrylimide-containing polymer of the present invention is an imidized product of a methacrylic acid ester polymer. The methacrylic acid ester polymer to be imidized is a methacrylic acid ester homopolymer or a copolymer of a methacrylic acid ester and a copolymerizable ethylenic monomer, and preferably has an intrinsic viscosity of 0.01 to 3.0. has.

Examples of the methacrylic ester constituting the homopolymer and copolymer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-methacrylate.
butyl, isobutyl methacrylate, ter methacrylate
Examples of acrylic esters include t-butyl, cyclohexyl methacrylate, norbornyl methacrylate, 2-ethylcyclohexyl methacrylate, and benzyl methacrylate; examples include methyl acrylate, ethyl acrylate,
Propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, norbornyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, and the like can be used. Examples of copolymerizable ethylenic monomers include methacrylic esters other than methacrylic esters, acrylic esters, acrylic acid, methacrylic acid, styrene, and substituted styrenes such as 2-methylstyrene. The above trimers may be used alone or in combination of two or more.

Among these methacrylic acid ester polymers, in the present invention, methyl methacrylate homopolymer or a copolymer of methyl methacrylate of 25 or more polymers and a copolymerizable ethylenic monomer of 75 or less polymers is used. is preferred. In particular, a homopolymer of methyl methacrylate is most preferred from the viewpoint of transparency.

The polymerization reaction and imidization reaction are performed in the presence of a solvent. The inert solvent used must not inhibit the progress of the heavy metals J, L, or the imidization reaction, and must not substantially react with the reaction mixture. In addition, in the case of a partial imidization reaction, it must not cause any change in the nistyl segment of methyl methacrylate or other methacrylic acid. Furthermore, it must be able to be easily separated and removed from the produced imidized polymer.

Preferred examples of the solvent include boiling points of 50 to 50 at normal pressure.
A mixed solvent of a poor solvent that does not easily dissolve the methacrylic resin at 150° C. and room temperature and a good solvent that easily dissolves the methacrylic resin is used. Preferably, the solubility parameter δ value of the solvent is 14.0 to 19.5 (cal/c
d) In the range of ``'', and as a good solvent) 8
Solvability parameter δ (direction is 8, O ~ 13.9 (ca
e/cl) ``'' range is used. An example of a poor solvent is methanol, and examples of good solvents are pentanol, he-1-zanol, 2-methylbenkenol, 4-methyl-2-pentanol, 2-ethyl-1-
Alcohols such as butanol, ■-pentanol, and octatool; aromatic hydrocarbon compounds such as benzene, toluene, -1-silene, ethylbenzene, cumene, mesitylene, naphthalene, tetraone, butylhenzene, diethylbenzene, pendelbenzene, and biphenyl; ho1'
Examples include ketones and ether compounds such as :1, isophoto, cyclo-kyrinone, acetophenone, schif'thyl ether, phenetol, methyl phenyl ether, diphenyl ether, diglyme, diethylene gnocol diethyl goether, and the like. Among these good solvents, toluene, benzene, xylene and ethylbenzene are preferred.

In addition, in the present invention, the solubility parameter δ (C.
Handbook. Second Ed, J.B.
randrup.

E. H. 1mmergutjohn Wiley &amp;
Sons, Neiv York) (1975).

In the mixed solvent used in the preferred production method, if the boiling point of the poor solvent and good solvent exceeds 150°C at normal pressure, volatile substances mainly composed of the solvent may be extracted from the reaction product obtained by the imidization reaction. It becomes difficult to remove it sufficiently. If the temperature is less than 50'C, the imidization reaction temperature cannot be raised due to an increase in the internal pressure of the reaction system, so a sufficient imidization reaction cannot be carried out, and the reaction product is volatilized. When separating and removing volatile substances, they suddenly volatilize, making it difficult to control the devolatilization operation. In addition, the solubility parameter δ of poor solvent and good solvent
If the combination of values is outside the above range, it will be difficult to perform a uniform polymerization reaction and a uniform imidization reaction, and it will be difficult to obtain a methacrylimide-containing polymer of excellent quality.

The amount of solvent used is based on the total weight of solvent and monomer.
Equipment at O ~ 60% double star. If the amount of solvent used is less than 10%, the viscosity of the reaction system will become too high, which will not only make handling difficult, but also cause the polymerization or imidization reaction to proceed unevenly, resulting in poor quality of the resulting polymer. Quality deteriorates. If the amount of solvent used exceeds 60% by weight, not only will it be difficult to separate the solvent from the IF polymer, but the amount of polymer obtained will be small, which will be disadvantageous for the T industry. Preferably, the amount of solvent used is 20-50%.

In addition, when using a mixed solvent, the ratio of poor solvent to good solvent is 99/1 to 1/99, preferably 90/10 to 10.
/90 (weight ratio).

In the imidization reaction, the inert solvent to be used allows the imidization substance to easily diffuse between the methacrylic polymers, so that the imidization reaction can be carried out uniformly and quickly, and also to suppress the heat generation and heat removal of the reaction. In order to enable effective control, it becomes possible to obtain transparent and heat resistant and methacrylimide-containing polymers as desired optical materials.

The radical polymerization initiator used during polymerization is one that actively decomposes at the reaction temperature and generates radicals.
er lebutyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, ter
tert-butyl perphthalate, tert-butyl perhenzoate, tert-butyl peracetate, 2
, 5-dimethyl-2,5-di(tert-butylperoxy)hexane, di-tert-amyl peroxide,
Organic peroxides such as 2,5-dimethyl-2,5-di(Lert-butylperoxy)hexane, benzoyl peroxide and lauryl peroxide, as well as abbisisobutanol diacetate, 1,1-azobiscyclohexanecarbo Nitrile, 2-phenylazo-
2,4-dimethyl-4-methoxyvaleronitrile, 2-
Cyano-2-propylazoformamide and 2,2'
-Ab compounds such as azobisisobutyronitrile are mentioned. These radical polymerization initiators can be used alone or in combination of two or more. The amount of radical polymerization initiator used is 0.0001 per monomer-containing solution.
-0.5% by weight.

Examples of the polymer molecule ff121M stabilizer include commonly used pullcaptans and others. Specific examples of mercaptans used include primary, secondary and tertiary mercaptans having alkyl groups or substituted alkyl groups, such as n-butyl, isobutyl, n-octyl, n-
-dodecyl, secbuti5ec-)decyl, 1er
t-Butyl mercaptan; aromatic mercaptans, such as phenyl mercaptan, thiocresol, 4-ter
tert-butyl-0-1,000-ocresol; 1,000-ocresol; 1,000-ocrecolic acid and its esters: 3-carbon atoms such as ethylene glycol, etc.
~18 mercaptans are mentioned. Further, as a non-mercaptan polymer molecular weight regulator, at least one of β-terpinolene, tilpinol, and alkyl-substituted-1,4-cyclohexadiene is used. As the alkyl-substituted-1,4=cyclohexadiene, γ-terpinene, 2-methyl-1,4-Schifl:1 hexadiene, 2゜6-dimethylcyclohexadiene, 2,5-dimethylcyclohexadiene, 2-isopropyl-1゜4
-cyclohexadiene, 2-ethyl-1,4-cyclohexadiene, and the like. The substantial amount of the polymer molecular weight regulator used is 5% by weight or less.

In a preferred continuous method for producing methacrylic acid ester polymers, the monomer solution described above is introduced into a substantially uniformly mixed first reaction zone and at a temperature of 60 to 190"C, at least the monomers are mixed. 40% by weight of is converted into polymer.

If the polymerization temperature in the first reaction zone is less than 60°C, the viscosity of the polymer will become low and it will be difficult to achieve uniform mixing. When the polymerization temperature exceeds 190"C, the formation of side reaction products increases.

Therefore, the polymerization temperature in the first reaction zone is 60-190'C
Preferably it is 70-180'C.

The conversion of monomer to polymer in the first reaction zone is 4
It has been found that when the amount is less than 0% by weight, the heat decomposition resistance of the finally obtained methacrylimide-containing polymer decreases.

Although the cause of this is not clear, it is presumed that it is due to a change in the terminal structure of the polymer molecule related to the polymerization termination reaction mechanism. When the thermal decomposition resistance of a polymer decreases, defects called silver streaks occur due to decomposition products during molding, which not only impairs the appearance but also deteriorates physical properties. Therefore, the polymerization conversion of the monomers in the first reaction zone is at least 40% by weight, preferably at least 60% by weight. The first reaction zone is not substantially uniformly mixed, and the polymerization conversion rate is 40% by weight in some parts.
If less than 20% of the total amount is present, the polymer having poor thermal decomposition resistance will partially form a polymer, so it is necessary to sufficiently mix and maintain a substantially uniform state in the first reaction zone. A substantially uniformly mixed reaction zone is typically achieved by using an agitated mixing vessel equipped with an anchor type, helical ribbon type, screw type, and paddle type agitator.

The polymerization solution leaving the first reaction zone is subsequently polymerized in a second reaction zone with plug flow at a temperature of 80°C to 170°C to form at least the 80-layer cavity of the initial monomer. converts into

The imidized substance (n) used in the third reaction zone partially reacts when the monomer remains to generate a high-boiling by-product amide derivative. If a large amount of unconverted monomer remains in the second reaction zone and enters the third reaction zone, the generation of the high-boiling byproduct amide derivative increases;
If the high-boiling by-product amide derivative remains in the polymer, it will cause coloration or quality deterioration of the polymer. In order to suppress the formation of derivatives, the polymerization conversion of the initial monomer in the second reaction zone is at least 8.
0% by weight, preferably at least 90% by weight.

In order to achieve a high polymerization conversion in the second reaction zone, a reactor with plug flow flow, i.e. a reactor having a relatively long shape, configured with feed from one end and discharge from the other end, is required. There is a need for a reactor that is designed so that there is no substantial mixing along the length of the device. Examples of this include the screw extruder type reactor described in U.S. Pat. No. 3,234,303;
2,950, U.S. Pat. No. 2,784
Examples include a tubular reaction device with a built-in shamakari and a hollow pipe-like reaction device described in No. 31.

The polymerization temperature in the second reaction zone is below 170'C.

For the reasons mentioned above, the polymerization conversion in the second reaction zone should be at least 80%; however, the highest polymerization rate achievable is due to the equilibrium between the propagation and reverse propagation reactions of the active polymer at a given temperature, i.e. It is controlled by the polymerization temperature, and if the polymerization temperature exceeds 170"C, it will be difficult to achieve a polymerization rate of 80%. On the other hand, if the polymerization temperature is less than 80"C, the polymerization rate will decrease, which is not economical, and the viscosity will be high. Therefore, the reaction temperature in the second reaction zone is 80 to 170°C, preferably 90 to 160°C, and -4
Ru.

The imidized substance represented by formula (n) above is added to the polymerization reaction solution exiting the second reaction zone, and the mixture is led to the third reaction zone.

The imidized substance used at this time may be used alone or after being dissolved and diluted in the above-mentioned inert solvent.

In the present invention, the raw material (methacrylic resin) and the formula (I
The imidization substance shown in I) needs to be substantially uniformly mixed before the imidization reaction.

If the imidization reaction proceeds without uniform mixing of the raw material methacrylic resin and the imidization substance, a nonuniform methacrylimide-containing polymer will be produced, and the imidization rate distribution width will essentially become large, which will reduce the transparency of the molded product. This leads to a decline in product value, including its quality. Further, even when blending with other types of thermoplastic polymers, homogeneous mixing becomes difficult and the physical properties of the polymer composition inevitably deteriorate.

As a result of intensive studies on such problems, the present inventors found that in the presence of the solvent required for the above-specified imidization reaction, the imidization reaction did not proceed and the raw methacrylic resin and the imidization substance were uniformly dissolved. Furthermore, it has been discovered that homogeneous methacrylimide-containing polymers can be produced industrially advantageously.

The above-mentioned uniform dissolution method includes a melting temperature of 50°C to 19°C.
It is important to stir at 0°C for at least 1 minute. At temperatures exceeding 190°C, the imidization reaction proceeds during mixing, resulting in a heterogeneous imidization reaction, resulting in a methacrylimide polymer that maintains a wide imidization rate distribution. On the other hand, if the temperature is less than 50°C, it will take time to mix and dissolve, and the viscosity of the solution will increase, which is disadvantageous as an industrial production method. Mixing and dissolving requires at least one minute. Stirring is required for mixing, but in the case of continuous production, it is necessary to mix while passing through a line using an in-line mixer or static mixer. If mixing in this area is insufficient, the resulting methacrylimide-containing polymer will have a wide imidization rate distribution, resulting in a mixture of various methacrylimide-containing polymers with different imidization rates, resulting in opacity. seriously impairing its industrial value. It is necessary that the imidization rate distribution width of the polymer is 5% or less.

More preferably, it is within 2%. In addition, if the solubility parameter δ value of the poor solvent and good solvent in the mixed solvent used in the above production method is a combination outside the range mentioned above, it will be difficult to achieve uniform dissolution, and as a result, it will be difficult to perform a uniform imidization reaction. , it is difficult to obtain methacrylimide-containing polymers of excellent quality.

The methacrylic polymer obtained in the second reaction zone and the imidized material are thoroughly mixed as described above and then reacted in the third reaction zone. This third reaction zone is composed of at least two reaction zones. One zone is a reaction zone where the methacrylic polymer and the imidized substance are reacted to cause a condensation reaction between the polymer side chains of the methacrylic polymer, and the other zone contains the imidized polymer. This is an aging reaction zone where the reaction product is further heated to further promote the imidization reaction. The imidization of the methacrylic polymer is carried out in at least two steps, the above-mentioned reaction zone and the ripening reaction zone, and it is also possible to carry out the process by combining multiple reaction zones and/or ripening zones as necessary. . The reaction between the methacrylate polymer and the imidized substance in the reaction zone is carried out at a temperature of 150°C or more and 350°C or less. When the reaction temperature is less than 150"C, the imidization reaction is slow and
If the temperature exceeds °C, a decomposition reaction of the raw material methacrylic polymer occurs simultaneously. The reaction time in the reaction zone is not particularly limited, but from the viewpoint of production, the shorter the better, it is in the range of 20 minutes to 5 hours.

Similarly, the average residence time in the case of continuous reaction is 20
The duration ranges from minutes to 5 hours.

In the imidization reaction, if water is present in the reaction system, the ester moiety of the methacrylic resin will be hydrolyzed by water as a side reaction during the imidization condensation reaction process, and as a result, methacrylic acid will be produced in the resulting methacrylic imide-containing polymer. As a result, it becomes difficult to obtain a methacrylimide-containing polymer having the desired amount of imidization, which is the object of the present invention. Therefore, this reaction is carried out under conditions in which the reaction system does not substantially contain water, that is, the water content is 1% by weight or less, preferably under anhydrous conditions.

Further, as for the atmosphere of the reaction system, from the viewpoint of coloring property of the imidized polymer obtained, it is preferable to carry out the reaction under an inert gas atmosphere in which nitrogen, helium, argon gas, etc. are present.

Specific examples of imidized substances represented by formula (II) include:
Aliphatic primary amines such as methylamine, ethylamine, propylamine, etc., and aliphatic primary amines such as 1,3-dimethylurea, 1,3-diethylurea, and 1,3-dipropylurea are generated by heating. Examples include compounds such as ammonia and urea. Also, aniline, toluidine,
Examples include aromatic amines such as trichloroaniline, and alicyclic amines such as cyclohexylamine and bornylamine.

Among the imidized substances used, methylamine, ammonia and cyclohexylamine are preferred from the viewpoint of heat resistance and transparency.

The amount of imidization substance to be used cannot be absolutely limited depending on the amount to be imidized, but methacrylic acid ester polymer 10
The amount is 1 to 250 parts by weight relative to 0 parts by weight. If it is less than 1 part by weight, no obvious improvement in heat resistance can be expected;
If it exceeds 50 parts by weight, it is unfavorable from the economic point of view.

The imidization reaction product taken out from the reaction zone is supplied to the aging reaction zone. The reaction in this aging reaction zone is carried out at a temperature of 150°C or more and 350°C or less, preferably 170°C or more and 300°C or less, similarly to the reaction in the previous step.

The aging time in the aging reaction zone is required to be at least 5 minutes, and when the aging is carried out continuously, the average residence time is also required to be 5 minutes or more. If the aging reaction takes less than 5 minutes, no obvious aging effect can be expected. Although the reason for the effect of the ripening reaction itself contributing to the product is not clear, if the ripening reaction is insufficient, unreacted amide segments remain in the imidized i7j coalescence product. Therefore, the heat resistance of the product itself, the heat decomposition resistance, and the degree of aberration after exposure to heat become remarkable.

The imidization amount of the methacrylic resin is such that the structural unit represented by the general formula (I) is 2 to 100% by weight, preferably 30 to 100% by weight, and more preferably 50 to 10% by weight from the viewpoint of heat resistance.
The amount should be within the range of 0% by weight.

The methacrylimide-containing polymer obtained by imidization has an intrinsic viscosity (the measuring method will be described later) of 0.02 to 4.5.

The reaction apparatus used to carry out the present invention is not particularly limited as long as it does not impede the purpose of the present invention, and includes a plug flow type reaction apparatus, a screw extrusion type reaction apparatus, a column type reaction apparatus, a back type reaction apparatus, and a back type reaction apparatus. A reactor, a duct-like reactor, a seed reactor, etc. are used. In order to perform imidization uniformly and obtain a uniform methacrylimide-containing polymer, a seed reactor equipped with a stirring device with a supply port and a discharge port that has a mixing function throughout the reactor is required. preferable.

After the imidization reaction is completed, the volatile matter is separated from the reaction solution to obtain the desired polymer. Vacuum flushing is performed while the reaction product containing a large amount of volatile matter is kept in a stable fluid state, and the volatile matter can be efficiently separated. That is, the reaction composition is heated to 180-300' C1, preferably 200-250°
Heat to a temperature of 20~10℃ and pass through a narrow nozzle
Flushing is performed in a tank regulated to a vacuum of 0 torr. The flashed polymer is received by the extruder screw and passed through the extruder to be obtained in the form of a strand from the die opening.

However, in the case of a screw type extruder, due to wobbling of the rotating shaft, contact with the barrel may occur, or a part of the screw may
Iron contamination occurs due to corrosion of the barrel. As a result of extensive studies, the inventor of the present invention found that the inclusion of iron tends to promote heat discoloration of the polymer, and when exposed to a high temperature atmosphere for a long time, the color changes to yellow, impairing the appearance of the product, and resulting in a decrease in transparency. I found out the truth.

This discoloration due to heat exposure becomes noticeable when the iron content in the polymer exceeds 20 ppm. Therefore, the iron content needs to be 20 ppm or less. More preferably, it is 10 ppm or less.

In order to reduce the amount of iron mixed in to 2 oppm or less, a portion of the extruder screw must be coated with corrosion-resistant chrome plating, and the screw portion itself must be made of superhard steel to prevent rotational shaft vibration. Additionally, the barrel portion needs to be made of corrosion-resistant stainless steel.

In the method of the present invention, additives such as antioxidants, plasticizers, lubricants, and ultraviolet absorbers may be added as necessary.

The advantages of the resin composition obtained by blending the methacrylimide-containing polymer of the present invention with other thermoplastic polymers are as follows:
The obtained composition is based on good heat colorability and better miscibility in terms of −C compared to a methacrylimide-containing polymer in which the iron content and imidization rate distribution are not specified. The objective is to demonstrate the properties of the film, including its surface gloss.

The methacrylimide-containing resin polymer of the present invention can be used with other thermoplastic polymers, such as ABS resin (copolymer of acrylonitrile-butadiene-styrene), MBS resin (copolymer of methyl methacrylate-butadiene-styrene), etc. ), methacrylic resin polymers containing methyl methacrylate as the main component, thermoplastic polyesters, modified and/or unmodified polyolefins, polyamides, polyphenylene oxides, polycarbonates, etc., resulting in good heat colorability and Provided is a resin composition that maintains good surface gloss.

Generally, the amount of methacrylimide-containing polymer made by the present invention can vary widely from 1% to 99% based on the total resin composition weight.

In addition to the above-mentioned thermoplastic polymer, other thermoplastic polymers may be used in combination, if necessary. Thermoplastic polymers used in combination include polystyrene, styrene/acrylonitrile copolymer, styrene/methyl methacrylate/acrylonitrile copolymer, α-methylstyrene/styrene/
Vinyls such as acrylonitrile copolymer, α-methylstyrene/methyl methacrylate/acrylonitrile copolymer, styrene/N-phenylmaleimide copolymer, p-methylstyrene/acrylonitrile copolymer, styrene/maleic anhydride copolymer, etc. Polymer, polyethylene, polypropylene, ethylene/butene-1 copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene 15-ethylidene-2-norbornene copolymer, ethylene/propylene/1.4 - Polyolefin rubbers such as hexadiene copolymer, ethylene vinyl acetate copolymer, and ethylene/butyl acrylate copolymer, and thermoplastic elastomers such as polyether ester, polyethyl ester amide, and polyether amide.

〔Effect of the invention〕

As explained above, the acrylimide-containing polymer of the present invention has a high degree of transparency and excellent heat resistance and heat colorability.

Therefore, it is widely used in fields where the above characteristics are required, such as optical fibers, optical disks, CRT filters, meters, displays for digital display boards, lighting optics, automobile headlight lamp covers, lenses, electrical parts, etc. can.

Blends with other thermoplastic resins can also be used in a wide variety of molding material applications.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples.

All references to "parts" and "1%" used in the examples are by weight.

In the following examples, the physical properties of the polymer were measured by the following method.

(I) The infrared absorption spectrum was measured using an infrared spectrophotometer (■
It was measured by the KBr disk method using Hitachi, Ltd. Model 285).

(2) Heat distortion temperature was measured based on ASTM D-648.

(3) The total light transmittance (%) of the molded product is ASTM D10.
It was measured by the 03 method. The sample is 40X40X3mm
An injection molded flat plate was used.

(4) Elemental analysis of the nitrogen content (x%) of the imidization rate polymer (measuring device CHN
Coder, MT-3 (manufactured by Yanagimoto Seisakusho)), and the imidization rate was calculated.

Example) Imidization rate X C.I.

(5) Imidization rate distribution Using the methacrylimide-containing polymer pellets produced in the method (4) as a population, 20 samples were arbitrarily taken from the population to determine the imidization rate distribution.

The maximum and minimum values in the distribution were taken as the imidization rate distribution.

(6) The yellowness index (YI value) can be determined using a color analyzer (
-710 to JIS standard using Hitachi Model 307)
Measured according to 3. A 40x40x3 injection molded plate was used as the sample. In the case of the methacrylimide-containing polymer resin, since it is a transparent material, the YI value was determined by measuring the transmitted light. Further, in the case of a resin composition consisting of a methacrylimide-containing polymer and another thermoplastic polymer, the YI value of the opaque material was determined by measuring the reflected light.

Calculated from X, Y, and Z stimulation values.

(7) Measurement of heating yellowing index (ΔYl) An injection molded flat plate (above 3M plate) of a methacrylimide-containing polymer and a composition consisting of this polymer and other resin polymers was placed in the air at 130°C for 1000 hours. (ΔYl) was measured after exposure to. - ΔY I =Y I -YIO ΔY■: Yellowing degree YI: Yellowness degree after exposure Ylo: Yellowness degree of the test sample or test piece (8) Iron content in the polymer Weigh 5 g of the polymer, After burning with a gas burner, melting in 6N hydrochloric acid water and making O,L normal hydrochloric acid aqueous solution, measure with a high-frequency plasma emission spectrometer (■ "1 Jarrell Ash") to determine the a content of iron. Ta.

(9) Measurement of surface gloss A resin composition obtained by mixing a methacrylimide-containing polymer and another thermoplastic polymer was formed into the above-mentioned flat plate (3 mm plate), and measured using a Murakami gloss meter according to JIS-Z- 874
Measured according to 1. Initial surface gloss was measured after molding.

Note that the intrinsic viscosity of the polymer is determined by Deelow-Bishop (Dee
The flow time (LS) of a dimethylformamide solution with a sample polymer concentration of 0.05% by weight and the flow time (LS) of dimethylformamide using a viscometer
to) at a temperature of 25±0.1°C, and ts/lo
The relative viscosity ηrel of the polymer is determined from the value, and then,
It is calculated from the following formula.

(In the formula, C represents the number of grams of polymer per 100 mj! of solvent.) Example 1 65 parts of methyl methacrylate, 30 parts of toluene, 5 parts of methanol, 0.08 parts of l,1'-abbiscyclohexanecarbonitrile, 2. A polymerization feed liquid consisting of 0.0325 parts of 2-abbisisobutyronitrile and 0.3 parts of N-octylmercaptan was continuously fed into the first stirred tank reactor having an internal volume of 2OL at a rate of 4L/Ilr. It was supplied continuously. The polymerization conversion rate was measured immediately after leaving the reactor and was found to be 65%.

This polymerization solution was introduced into a second multi-tubular heat exchange type reactor (consisting of 30 wood straight pipes with an inner diameter of 12.7 mm and a length of 10,100 O+), and was heated to 95% at a temperature of 140°C. Polymerization was allowed to proceed until the polymerization conversion rate was reached. Furthermore, this polymerization liquid was mixed with the following imidized substance and supplied to the stirred tank type reactor in the third reaction zone.

On the other hand, methylamine was added to a mixed solvent (toluene:methanol - 1:1 weight ratio) in which the imidized substance (methylamine) was dissolved and diluted to make 40% by weight, and the amount was 1.2L/llr.
The mixture was mixed with the polymerization solution and supplied to the third reaction zone. The temperature of the imidized substance and the polymerization solution was such that the loo'c residence time was 5 minutes, and after sufficient mixing using an in-line mixer, the mixture was supplied to the third reaction zone. The mixed liquid of the polymerization liquid and the imidization substance was placed in the third reaction zone (inner volume 15 L, temperature 23
After the imidization reaction was carried out by supplying the reaction solution to a stirred reactor at 0'C), the reaction solution leaving this reaction zone was heated to an internal volume of 3 L and a temperature of 23.
The mixture was supplied to a stirred tank type reactor which serves as a 0°C aging reaction zone.

The reaction liquid leaving these reaction zones is flushed from the nozzle port into a tank regulated under a reduced pressure of 100 torr.
The flushed polymer was supplied onto a L/D20 screw, extruded into a strand shape using a 30φ double vented twin-screw extruder, and pelletized. The extruder with double vent has a vent part vacuum level of 5 mmHg and a temperature of 260'C.
, metal ring temperature 270°C, die temperature 255°
It was set as C. When the infrared spectrum of the obtained pellet-like polymer was measured, the wave number was 1720 cm-', 166.
Absorption peculiar to methacrylimide was observed at 3cm-' and 750c', confirming that it was a methacrylimide-containing polymer.A part of the screw inside the extruder was chrome-plated, and the barrel part was made of stainless steel. did.

The physical properties of the polymer are as follows.

Total light transmittance (%) 93 Heat distortion temperature ('C) 145
Imidization rate (%) 80 Imidization rate distribution width (%) 1.5 Y I O, 5Δ
Y I
Iron content N in O,9 polymer (pp thin) 0.8
As described above, a methacrylimide-containing polymer was obtained that had excellent transparency and heat resistance, and was also excellent in heat coloring and coloring over time.

Comparative Example 1 Polymerization and imidization were carried out in the same manner as in Example 1 using the same monomer composition, imidization material composition, and apparatus. However, when mixing the polymerization liquid and the imidization substance exiting the second reactor, the imidization reaction is carried out without using an in-line mixer, and the barrel part in the extruder is made of nitriding steel, and the screw part is made of nitrided steel. The procedure was the same as in Example 1 except that one without chrome plating was used.

The physical properties of the obtained polymer are as follows.

Total light transmittance (%) 86 Heat distortion temperature ("C) 145
Imidization rate (%) (average value) 80 Imidization rate distribution 11 (%) 7゜5Y
I 3.2ΔY
1
9.0 Iron content fi (ppm) in polymer
23.0 As described above, the resulting polymer was prepared in Example 1.
The transparency was poorer, and the coloring and change over time under heating were poorer than that of the above.

Example 2 A monomer mixture consisting of 100 parts of methyl methacrylate monomer, 0.1 part of 1.1'-azobiscyclohexane carbonitrile polymerization initiator, and 0.5 part of n-octylmercaptan polymerization degree regulator was heated at 100° C. for 17 hours to obtain a raw material (methacrylic resin). The polymerization conversion rate was 99%.

A mixture of 100 parts of the above methacrylic resin and 80 parts of toluene and 20 parts of methanol as solvents was placed in an IOL reactor equipped with a Battle Viral stirrer, a pressure gauge, a sample injection container, and a jacket heater, and the atmosphere was sufficiently purged with nitrogen. After that, the temperature was raised to 150°C and stirred to melt the polymer.Next, 18.6 parts of methylamine (0,
6 molar ratio) was dissolved in methanol to make a 50% solution, added at a temperature of 150°C in the reaction vessel, heated and stirred for 30 minutes, and then raised to 230'C with an internal pressure of 60 kg/cd -
G for 3.0 hours.

After the reaction is completed, the N-methylmethacrylimide-containing polymer solution is flushed from the nozzle opening into a tank adjusted to a vacuum of too much, and the flushed polymer is
The mixture was fed onto a 30φ bent extruder screw with L/D20, and shaped into a strand by the extruder. Part of the screw inside the extruder is chrome-plated, and the barrel is made of stainless steel.

When the infrared absorption spectrum of the obtained polymer was measured, the wave numbers were 1720 cm-', 1663 cm-' and 7.
Absorption characteristic of methacrylimide-containing polymers was observed in 50c "1.Extruder equipment conditions: Vent section vacuum level: 5 mm, 11 g
The extrusion conditions were a temperature of 260°C, a metal ring zone of 270°C, and a die part temperature of 255°C.

The physical properties of the obtained polymer are as follows.

Total light transmittance (%) 93 Heat distortion temperature ('C) 145
Imidization rate (%) 80 Imidization rate distribution (%) 1.8 YIl, 5 ΔY I 1.3
Iron content in polymer (ppm) 1.
0 As described above, a methacrylimide-containing polymer was obtained which had excellent transparency and heat resistance, as well as excellent heat coloring and heat coloring properties.

Examples 3 to 14 The methacrylimide-containing polymer produced in Example 1 and various thermoplastic polymers were mixed in a 30φ diameter extruder (screw; chrome plating specification, barrel,
After melt-kneading using stainless steel (stainless steel specifications), it was pelletized. The extrusion temperature was 290"C. The obtained pellet was dried in vacuum and then injection molded into a test piece 12 for measuring physical properties.
Molded.

The cylinder temperature was variable from 260°C to 300°C, and the mold temperature was 90°C.

The measurement results are shown in Table-1.

Preparation of other thermoplastic polymers ABS: Emulsion graft copolymerization of acrylonitrile and styrene in the presence of butadiene latex, rubber-containing 160
%.

MBS: Rubber content 5 by emulsion graft copolymerization of methyl methacrylate and styrene in the presence of butadiene latex.
It was set to 0%.

PMMA: P, %i By the polymerization method, methyl methacrylate was radically polymerized using a benzoyl peroxide initiator.

PET: Polyethylene terephthalate was obtained by a condensation reaction from terephthalic acid and ethylene glycol.

PBT: Polybutylene terephthalate was obtained by a condensation reaction from terephthalic acid and 1.4-butanediol.

Unmodified polyolefin (PP): 70% ethylene,
Ethylene-propylene copolymer consisting of 30% propylene.

Modified polyolefin (modified pp): 0.03 part of α, α'-bis-t-butyloxy p--1-benzene dissolved in a small amount of acetone per 100 parts of polyolefin (the above-mentioned ethylene-propylene copolymer) and A modified polyolefin was obtained by kneading the mixture with 1 part of maleic anhydride using an extruder.

Polyamide: N11 6,6612 made by melt polymerization method
I got it.

Nylon 6 is ε-cabrolacta J, from nylon 6
6 was obtained from hexamethylene diamine and adipic acid, and nylon 12 was obtained from 12-aminododecanoic acid.

Polyphenylene autoside dinonyl 731J (manufactured by GE) was used.

Polycarbonate Nilexane+41 (manufactured by GE) was used.

Comparative Examples 2 to 13 The methacrylimide-containing polymer produced in Comparative Example 2 and various thermoplastic polymers were blended at the blending ratios shown in Table 2, and molded in the same manner as Examples 3 to 14.

The physical property measurement results are shown in Table-2.

In comparison with Examples 3 to 14, it was found that all cases were inferior in heat coloring, color change, and surface gloss.

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R is a hydrogen atom or an aliphatic group having 1 to 20 carbon atoms,
A thermoplastic polymer consisting of 2 to 100% by weight of structural units represented by (representing an aromatic or alicyclic hydrocarbon group) and 0 to 98% by weight of structural units derived from an ethylenic monomer. A methacrylimide-containing polymer having an iron content of 20 ppm or less and an imidization rate distribution width of 5% or less in the polymer. 2. A resin composition comprising 1 to 99% by weight of the methacrylimide-containing polymer according to claim 1 and 99 to 1% by weight of another thermoplastic polymer. 3. Other thermoplastic polymers include a copolymer consisting of acrylonitrile-butadiene-styrene (ABS resin), a copolymer consisting of methyl methacrylate-butadiene-styrene (MBS resin), and methacrylate whose main component is methyl methacrylate. The resin composition according to claim 2, which is selected from resin polymers, thermoplastic polyesters, modified and unmodified polyolefins, polyamide resins, polyphenylene oxides and polycarbonates.