JPS6164703A - Production of methacrylimide-containing polymer excellent in transparency and heat resistance - Google Patents

Abstract

PURPOSE:To obtain the titled polymer excellent in mechanical properties, transparency and heat resistance, by separating volatile matter from a reaction product obtained by reacting a methacrylic resin with a specified compound in the presence of a nonpolymerizable solvent and a reaction catalyst. CONSTITUTION:A reaction product is obtained by reacting a methyl methacrylate (co)polymer (A) of an intrinsic viscosity of 0.01-3.0 with at least 10wt%, based on component A, compound (B) of formula I (wherein R is H or R1) as an imidating compound at 100-350 deg.C in the presence of a nonpolymerizable solvent (C) of a solubility parameter delta of 8.5-15.0(cal/cm<3>)<1/2> (e.g., methanol) in an amount of provide a component A concentration of 20-80wt% and at most 20wt%, based on component B, tert. amine compound (D) of formula II (wherein R1-3 are each 1-10C aliphatic, aromatic or alicyclic hydrocarbon group) as a reaction catalyst and, optionally, an antioxidant, while maintaining the water content in the reaction system at 1wt% or below. Volatile matter is removed from this reaction product by, e.g., a vented extruder to obtainer the titled polymer of a residual volatile matter content <=1wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a nine-methacrylimide-containing polymer having excellent transparency and heat resistance.

(Prior art) Methyl methacrylate polymers are used as high-performance plastic optical materials and decorative materials because of their excellent not only transparency but also mechanical properties and weather resistance.In recent years, they have been used in short-distance optical communications, Development of applications for minute meters such as optical sensors is underway.

However, methyl methacrylate polymer has a thermal deformation degree of 1.
Due to its insufficient heat resistance of around 0C1℃, its application development is restricted in many fields.

There is a strong demand for improved heat resistance.

As a method for improving the heat resistance of methyl methacrylate polymer, there is a method of imidizing the methyl methacrylate polymer. Patent No. 2.1
4 Gourd No. 209, German Patent No. 1077872, German Patent No. 1
No. 242,369], a method in which a methyl methacrylate polymer is totally reacted with ammonium hydroxide, ammonium phosphate, and an alkyl amine (U.S. Pat. No. 3,284,42).
No. 5, British Patent No. 926,629] and a method of reacting an acrylic acid polymer with ammonia or a primary amine [US Pat. No. 4,246,374] #.

However, although the heat-resistant shapeability of the imidized polymer obtained by the above method is improved, there are concerns that the transparency may be poor, the molecular weight may be substantially reduced, or the imidization may be non-uniform. Therefore, it is inferior in mechanical properties, optical properties, colorability, moldability, etc., and has not yet been put into practical use.

(Problems to be Solved by the Invention) The first object of the present invention is to
Excellent optical properties inherent to methyl methacrylate polymer,
The object of the present invention is to provide a method for producing a nine-methacrylimide-containing polymer that has properties such as mechanical properties, weather resistance, and moldability, and has excellent transparency and heat resistance.

A second object of the present invention is to provide a method for producing a methacrylimide-containing polymer of excellent quality and in which the imidization reaction can be easily controlled.

A third object of the present invention is to provide an industrially advantageous method 1 for producing a methacrylimide-containing polymer.

[Means for solving problems]

The method for producing a methacrylimide-containing polymer having excellent transparency and heat resistance according to the present invention uses a methacrylic resin and a methacrylic resin having the following general formula: ,
The ring group represents an aromatic hydrocarbon group) (hereinafter referred to as "imidized substance") was heated at 100°C in the coexistence of a non-polymerizable solvent and a reaction catalyst.
The process consists of reacting at a temperature above 350° C. and then separating and removing volatile substances from the obtained reaction product.

The "methacrylimide-containing polymer" used in the method of the present invention refers to a methacrylic resin in which a methacrylimide segment is introduced into the polymer side chain.

The "methacrylic resin" used in the method of the present invention refers to a methyl methacrylate homopolymer having an intrinsic viscosity of 001 to 50, or a combination of methyl methacrylate and an acrylic ester of up to 75% by weight. Examples of acrylic esters include ethyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylic powder, acrylic ester, etc. As the methacrylic ester such as 2-ethylhexyl methacrylate and benzyl acrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylcycloheyacyl methacrylate, benzyl methacrylate, etc. can be used. These single dragon bodies can be used alone or in combination of two or more.

The present invention can be roughly divided into two steps: reaction process and volatile substance separation. ), the reaction step is a step in which the methacrylic resin and the imidized substance are reacted to cause a condensation reaction between the polymer side chains of the methacrylic resin. The volatile substance separation step is a process of separating and removing volatile substances, the main component of which is a non-polymerizable solvent, from the reaction product containing the imidized methacrylic resin produced in the reaction process.

In the reaction step, preferably, the methacrylic resin and the imidized substance are mixed in the coexistence of a non-polymerizable solvent and a reaction medium, and the imidized substance and a mixture of the methacrylic resin dissolved in the non-polymerizable solvent are combined in a non-polymerized manner. The reaction is carried out in the coexistence of a neutral solvent and a reaction catalyst.

In the reaction process, the non-polymerizable solvent used is:
In the case of a partial imidization reaction, the methyl methacrylate must be one that does not affect the methacrylic acid ester segment without inhibiting the imidization reaction, which is a condensation reaction between polymer side chains. be. Examples include alcohols such as methyl alcohol, methyl alcohol, isopropyl alcohol, and methyl alcohol; benzene,
Aromatic hydrocarbon compounds such as toluene, xylene; methyl ether ketone, glyme, diglyme, dioxane,
Ketone-like ether compounds such as tetrahydrofuran;
Examples include dimethylformamide, dimethylsulfoxide, and dimethylacetamide. F of non-polymerizable solvent
I folding parameter δ value (Polymer Handbo
ok, 8econdEd, J.

Brandrup, E., H. Immergut,
John WileyTo 5ons, New
York, 1975] is a5~15.0 (cal
/m ) is preferably in the range of less than 85 and t5. of: Those exceeding the solubility are insufficient.

The above-mentioned non-polymerizable solvent used in the present invention allows the imidization substance to easily diffuse between the polymer chains of the methacrylic resin, allowing a uniform imidization reaction to occur quickly, and controlling heat generation and heat removal during the reaction. Effect: It has the effect of dissolving imidized substances and adjusting the viscosity of methacrylic resin.

The amount of non-polymerizable solvent used in the method of the invention is:
From the viewpoint of productivity, it is better to have a smaller amount, but if it is too small, the effect of the non-polymerizable solvent will be reduced, so a range of 20 to 80 weight f% is preferable.

The imidized substances represented by the general formula CI) used in the method of the present invention include primary amines such as methylamine, etelamine, and propylamine; 1,3-dimethylurea, 1,3-diethylurea, Examples include compounds that generate primary amines when heated such as 1.3-dipropylurea, ammonia, and urea. The amount of these compounds to be used cannot be limited to one amount depending on the amount to be imidized, but is in the range of 10 weight tons or more based on the methacrylic resin. 10
If the amount is less than % by weight, no obvious improvement in heat resistance can be expected.

The reaction between the methacrylic resin and the imidizing agent in the reactor is 1
00℃ or higher and lower than 350℃, preferably 150℃ or higher and 30℃
It is below 0°C. Reaction 1? When the temperature is less than 100°C, the silimidation reaction is slow, and when it exceeds 350°C, a decomposition reaction of the i'j4 methacrylic resin occurs simultaneously. The reaction time is not particularly limited. .

In the reaction, if a large amount of water is present, the ester moiety in the methacrylic acid Medel segment will undergo hydrolysis with water as a side reaction during the imidization condensation reaction process, resulting in the production of methacrylic acid. It becomes difficult to obtain a methacrylimide-containing polymer having an imidization amount of . Therefore, in this reaction, it is preferable to carry out the reaction under substantially no water-containing conditions, that is, under conditions where the water content is 1% by weight or less, preferably under anhydrous conditions.

The amount of imidization of the methacrylic resin in the present invention can be arbitrarily determined, but from the viewpoint of heat resistance, it is preferably 10% or more.

As a reaction catalyst, the following general formula (in the formula,
R1, R2, R13 are the same or different carbon numbers 1 to 10
A tertiary amine conductor represented by (representing an aliphatic, aromatic, or alicyclic hydrocarbon group) is used. Examples include trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, dimethyl-p-toluidine, lutidine,
Examples include pyridine, picoline, and quinoline.

The amount of reaction catalyst to be used varies depending on the amount of imidized material to be used, but is generally not more than 20 parts by weight, preferably not more than 10 parts by weight, based on the imidized material.

In the reaction process of the present invention, first, the side chain ester moiety and 1
It is thought that the reaction route is that amidation occurs through reaction with a secondary amine, followed by imidization. The above-mentioned reaction catalyst shows a surprising effect of accelerating the reaction of converting amide into imide. Particularly when the purpose is a partial iodization reaction, S exhibits the effect of accelerating the imidization of segments existing as amide intermediates. Thus, it is possible to shorten the imidization reaction time and conduct the imidization reaction at a low temperature only by using a combination of the non-polymerizable solvent and the reaction catalyst.

The reaction equipment 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 may include a plug flow type reaction equipment, a screen extrusion type reaction equipment, a column type reaction equipment, etc. Examples include a tube-type reaction device, a duct-like reaction device, a tank-type reaction device R, and the like. In particular, in order to uniformly perform imidization and obtain a uniform methacrylimide-containing polymer.

It is preferable to use a seed type reactor equipped with a stirring device having an outside supply port and a discharge port, and which has a mixing function throughout the inside of the reactor.

In the volatile substance removal step, most of the volatile substances are separated and removed from the reaction product containing the intermolecular condensation reaction product by the reaction between the methacrylic resin and the imidized substance. The content t of residual volatile substances in the final polymer is preferably less than α1 weight under an electric field. Removal of volatile substances can be carried out using a common vent extruder, devolatizer, etc., or by other methods, for example, the reaction product f: diluted with FI medium and precipitated in a polyelectroinsoluble medium. , filtration and drying methods, etc. may be used.

In the method of the present invention, the molecular weight is reduced by radical depolymerization of the raw material methacrylic resin under high temperature reaction.
: It is preferable to add an anti-oxidant to the evening scene to avoid lingering licks.

Antioxidants include tricresyl phosphite, cresyl 78yl phosphite, tributyl phosphite, and tripyl sulfite) =? Specific examples include phosphite-based antioxidants based on phosphite esters such as diethyl; hindered phenol-based antioxidants such as hydroquinone, cresol, and phenol derivatives; naphthylbutane and dialkyl disulfide derivatives.

Furthermore, other additives such as plasticizers, lubricants, ultraviolet absorbers, colorants, pigments, etc. may also be added depending on the performance requirements of the product.

The method of the present invention can be carried out either continuously or batchwise.

Next, a typical apparatus used in carrying out the present invention will be described with reference to FIG.

The non-polymerizable solvent containing the reaction catalyst flows from solvent storage tank 1 to line 2.
is sent to the solvent supply tank 4 by the pump 3, and the antioxidant, which is added as necessary, is supplied from the antioxidant storage tank 5 through the line 6 to the solvent supply 4g4, where it is intoxicated, and then sent to the resin dissolution tank. Sent to 10.

On the other hand, resin is supplied from the pellet storage tank 8 to the resin melting tank 10 through a line 9. The resin melting tank 10 has a stirrer 11 and a jacket 12, and a heat medium flows through the jacket through openings 13 and 14. The melted resin in the resin melt 1a10 is discharged through the discharge line 15, pump 16, and line 17.
is sent to the reaction tank 20 and imidized substance storage 1a18
It is reacted in a reaction tank 20 with a hexaimidized substance supplied from the above.

A reaction tank 20 is equipped with a spiral ribbon type stirrer 21 and a jacket 22.
It will be distributed through the deceased and 24. The reaction product in the reaction tank 20 is sent to the thermal formation tank 28 via a discharge line 25, a pump 26, and a line 27t.

Mature#! A 28-piece spiral ribbon stirrer 29 and a jacket 30t (a heat medium is allowed to flow through the openings 31 and 32 in the jacket). The aging reaction product is passed through the discharge line 33, the pump 34, and the line 35f.
The volatile matter is sent to the machine 36, where the volatile matter is removed.
It is discharged from 37.

The volatile separator 36 is equipped with a screen and -38% vent 39 and a heating means 40f.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples.

All parts and parts used in the examples are by weight. The device system shown in FIG. 1 has the following specifications.

Resin dissolution tank 500 is a reaction tank 401 Aging tank 201 Volatile separator single screw screw, - Pent extruder screen, -; 305 mφ x 720 - Long pent length: 60 m Based on these actual examples, a method for measuring the characteristics of one unit by the following method.

(1) The infrared absorption spectrum was measured by the KBr disk method using an infrared spectrophotometer (@Hitachi New Model 285).

(2) The intrinsic viscosity of the polymer is
reax -B15choff) Polymer concentration FR0.5 weight tested by viscometer! The flow time (ts) of renal dimethylformamide solution and the flow time (to) of dimethylformamide were measured at a temperature of 25 ± 11 °C, and tl
Determine the relative viscosity of the polymer from the /lo value,
After that, it is a value calculated from the following formula.

Intrinsic viscosity ffz (In W reI ) / C (where C represents 100 grams of solvent minus the number of grams of polymer) (3) Heat deformation a beak was measured based on A3TMD64B.

(4)! The melt index of the coalescence is ASTMD
Calculated using l 2!18 (t number for 10 minutes at 230°C and a load of 9 Kf).

(5) The total light transmittance (2)-jii- and haze value (%) of the molded article were measured.

(6) The imidization t('j) of the x combination was determined from the nitrogen content using elemental analysis NI (measuring device CHN coder (M'r-3) manufactured by Yanagimoto Seisakusho).

(7) Measurement of the amide profile (π) of the polymer is performed using proton NMB.
It was determined by measurement (FX-90 JEOL).

Example 1 Sufficiently dried methyl methacrylate polymer (Acrivet (trademark) VH, manufactured by Mitsubishi Rayon@).

Intrinsic viscosity = 0.51) 100 parts, dehydrated and dried toluene 90 parts, dehydrated and dried methanol 10 parts, antioxidant (manufactured by Yoro Kagaku Kogyo@, ANTAGE (trademark) BHT, chemical name t
ert, -butyl-P-yvsol] α01 part, trinibulamine (11 parts) was mixed into 500 tons of raw material.
The polymer was placed in a dissolving tank and was dissolved at 200° C. while stirring.

Next, this solution was continuously fed into the reaction tank at a feed rate of 51 part hours, and the temperature inside the tank was adjusted to 230° C. while stirring thoroughly at a stirring speed of 1 and 90 rDm. after that,
Dry methylamine was continuously fed into the reactor at a rate of 20 mol/hour, and the circular pressure was 751 g/g/g. The temperature in the reactor was maintained at 230°C during the reaction, and the average residence time was t. -1,0 hours and 6.

The reaction product taken out from this reaction tank is pumped,
The mixture was placed in an aging tank and aged with sufficient stirring for an average residence time of t-11.5 hours, with the aging temperature set at 230°C. The aged reactant was continuously fed to a pent extruder to separate and remove volatile substances. Warm honey from vent extruder is pen l@230
℃, extrusion @ 230℃, vent part vacuum honey 9 w Hg s
I made it bg. After cooling the strand extruded from the die with water, it is cut to obtain a pellet-like polymer having good transparency.

On the other hand, toluene, methanol, and unreacted methylamine discharged from the vent section should be cooled and collected.

When the infrared absorption spectrum of the obtained telepolymer was measured, the wavenumbers were 1720aR, 1663m-' and 750aR.
Absorption characteristic of methyl methacrylimide polymer is observed at ℃M, elemental analysis also shows a nitrogen content of 3%, NMR measurement shows absorption corresponding to methyl methacrylimide, and intermediate methyl methacrylic No absorption corresponding to imide was observed, imidization: [t=
10 Q%, and it was confirmed that the polyN-methylmethacrylimide polymer was almost completely used.

We also evaluated the physical properties of this polymer and found that it had the following properties.

Intrinsic viscosity: 148 Melt index: 1.7 Thermal deformation wetness: 182°C Total light droplet conductivity: 95. Examples 2 to 30 Various methacrylimide-containing polymers were produced using the same method as the apparatus of Example 1 using methacrylic resins and imidized substances as shown in Table 1. I regret it. The pressure inside the reaction tank 8E was set at 20-45/1.gauge pressure.

Table 1 shows reaction results and evaluation results of the nine polymers obtained *1 Methyl methacrylate polymer (intrinsic viscosity = 1.so) *2 Tert, -butyl methacrylate (intrinsic viscosity = 1
．． 15) *3 Methyl methacrylic acid copolymer (
Weight ratio = 9515, intrinsic viscosity = 1, 20) *4 Methyl methacrylate-methyl acrylic copolymer (weight ratio = 9515, intrinsic viscosity = 0.35) *5 Methyl methacrylate-acrylic hflj copolymer゛('A ratio = 9515, intrinsic viscosity = 1.2Ll) *6
Methyl methacrylate-acrylic 0-butyl copolymer (weight ratio = 90/10. Intrinsic viscosity = 1.00) *7 Menal methacrylate-methacrylic lees enal-methacrylic acid copolymer (weight ratio = 901515, intrinsic viscosity =
1,50) *8 Methyl methacrylate-acrylic acid tert, -buna-methacrylic tert, -butyl copolymer (
Weight ratio = 901515, intrinsic viscosity = j, 05) *9 Methyl methacrylate-acrylic "$tert, -
Butyl copolymer coelectropolymer = i, 20, solid neck viscosity change 21
．． 20) *10 Menalousterene methacrylate copolymer (heavy/cyclized = 80/20, intrinsic viscosity = 1.05) *11 Methyl methacrylate-benzyl methacrylate copolymer (weight ratio = 90/10, intrinsic viscosity = cL95
) Hata 12 Methyl methacrylate-cyclohexyl methacrylate copolymer (weight ratio = 90/1Q, intrinsic viscosity = 1.
00) Jar 13 Actual M6 Same example 3 as the one used in example 1
1. In a 10 t reactor Z5 equipped with a paddle spiral stirrer, a pressure gauge, a sample injection container, and a Jafut heater, sufficiently dried methacrylic methyl polymer (acrypet (cloth q) V
H, Mitsubishi Rayon's Cape, intrinsic viscosity q = 0.513100g
, 90 parts of dry toluene, 10 parts of dehydrated and dry methanol, and an antioxidant (manufactured by Teva Geigy, Irganox (
1076) A mixture of 1 part of Q and 0 was added, and after sufficient nitrogen exchange, the temperature was raised to 230°C and the mixture was stirred and kneaded to dissolve the polymer.

Next, at 230° C. ms, 12.4 parts of methylamine (0.4 molar ratio), Tri-1-TeA were added from the reagent injection container.
, 7min 1.01 @ [cL01 molar ratio] T-dried methanol was added in 50 copies, and the internal pressure was 26Kf/c.
Incubate the reaction at rs gauge pressure for 1.5 hours.

After the reaction is completed, the methacrylimide-containing polymer solution is reprecipitated with n-hexane, and then ? Filter and dry in a reduced EE dryer at 70°C to obtain a white powdery polymer.

When the infrared absorption spectrum of this obtained polymer was measured, the fpi numbers were 1720, 1663/M, and 7.
Absorption characteristic of methacrylimide was observed in 501M, and it was confirmed that it was a methacrylimide-containing polymer. Table 2 shows the evaluation results of the physical properties of this polymer.

Examples 32 to 44, Comparative Examples 1 to 8 Implemented under the conditions shown in Table 2. A number of polymers were produced by repeating the method of J51, which had a rating of 5: 9.

ibf'l＆FjMt""2 @K 7F"',
° Below blank space (effects of the invention) According to the method of the present invention, it is possible to easily control the imidization reaction, and to industrially advantageously produce a methacrylimide-containing polymer of excellent quality. This polymer has excellent transparency and heat resistance. Therefore, it can be used in fields where such properties are required, such as C11, T filters, television filters, fluorescent tube filters, liquid crystal filters,
It can be used in a wide range of applications such as meters, digital display boards and other displays, lighting optics, headlight covers for automobiles, electrical parts, etc., and has great industrial significance and value.

[Brief explanation of the drawing]

FIG. 1 diagrammatically shows an example of an apparatus used in the practice of the invention. In the figure, 10 is a finger melting tank, 20 is a reaction tank, 28 is a ripening tank, and 36 is a volatile substance separation device.

Claims (1)

[Scope of Claims] 1. Methacrylic resin and the following general formula B-NH_2 [I] (wherein R is H or a hydrocarbon group having 1 to 10 carbon atoms which is aliphatic, alicyclic or aromatic) ) in the coexistence of a non-polymerizable solvent and a reaction catalyst.
A method for producing a methacrylimide-containing polymer having excellent transparency and heat resistance, which comprises reacting at a temperature of .degree. C. or higher and lower than 350.degree. C., and then separating and removing volatile substances from the resulting reaction product. 2. Solubility parameter δ of non-polymerizable solvent is 8.5 to 1
5.0 (cal/cm^3)^1^/^2 The method for producing a methacrylimide-containing polymer having excellent transparency and heat resistance according to claim 1. 3. The reaction catalyst has the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [II] A method for producing a methacrylimide-containing material having excellent transparency and heat resistance according to claim 1, which represents a hydrocarbon group of the group (1).