JPH02142802A - Manufacture of methacrylimide-containing polymer excellent in transparency and heat resistance - Google Patents

Abstract

PURPOSE:To produce a polymer excellent in optical properties, moldability, etc., and having high transparency and heat resistance by reacting a methacrylate resin with an imidated compound in the presence of a specific mixed solvent, and removing volatile materials. CONSTITUTION:A methacrylate resin is reacted with a compound of formula I (wherein R is H, or a 1-20C aliphatic, aromatic or alicyclic hydrocarbon group) at 100-350 deg.C in the presence of a mixed solvent comprising a poor solvent which has a boiling point of 50-135 deg.C at ordinary pressures and hardly dissolves the methacrylate resin at ordinary temperatures and a good solvent which as a boiling point of 135-260 deg.C at ordinary pressures and easily dissolves the methacrylate resin at 100-350 deg.C. Then, volatile materials are separated and removed from the reaction product to obtain the aimed methacrylimide- containing polymer which comprises 2-100wt.% constituent units of formula II and 0-98wt.% constituent units derived from the ethylenic monomer.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing a methacrylimide-containing polymer having excellent transparency and heat resistance. [Prior art] Methyl methacrylate polymer is used as a high-performance plus deck optical material and decorative material due to its excellent not only transparency but also mechanical properties and weather resistance.In recent years, it has been used for short-distance optical communications, optical sensors, etc. Application development is being pursued in various fields. However, methyl methacrylate polymer has a heat distortion temperature of around 100'C1 + 11iJ for less than 1 minute, so its use is limited in many fields, and there is a strong demand for heat resistance. As a method of improving the heat resistance of methyl methacrylate polymer, there is a method of imidizing a methyl methacrylate polymer.
A method of conducting a thermal decomposition condensation reaction with a class amine (U.S. Patent No. 2,
416,209), a method of reacting a methyl methacrylate polymer with ammonium hydroxide, ammonium phosphate and al-1-lamine (British Patent No. 926,629), and a method of reacting a methyl methacrylate polymer with ammonia or primary Method of reacting with amines (U.S. Pat. No. 4,246.37)
No. 4) has been proposed. ``Inventive Power R1'' Problem to be Solved) However,
The imidized polymer obtained by the above proposed method still contains a breaking point without any improvement, and therefore has excellent optical properties, mechanical properties, weather resistance, moldability, etc. It is desired to develop a methacrylimide-containing polymer that has the following properties and has a high degree of transparency and heat resistance M. [Means for Solving the Problems] The method for producing a methacrylimide-containing polymer according to the present invention comprises combining a methacrylic resin with the general formula % (1) (where R is a hydrogen atom or a fatty acid having 1 to 20 carbon atoms). family,
aromatic or alicyclic hydrocarbon group) with a boiling point of 50 to 135°C under normal pressure.
In the presence of a mixed solvent of a poor solvent that is difficult to dissolve methacrylic resin at room temperature and a good solvent that has a boiling point of more than 135°C and less than 260°C and that dissolves methacrylic resin at normal pressure, The reaction is carried out at a temperature of 350° or lower than C, then the volatile substances are separated and removed from the resulting reaction product, and the reaction is carried out at a temperature of 1) 1ζ (where R is as described above). ) to obtain a methacrylimide-containing polymer with excellent transparency and heat resistance consisting of 2 to 10% of structural units (1%) and 0 to 913% of structural units derived from enolene (I monomer) The method of the present invention involves reacting (! R represents a hydrogen atom or an aliphatic, aromatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms.Specific examples of imidized substances include monoammonium; methylamine, ethylamine, Examples include aliphatic primary amines such as 11-pyramine; aromatic amines such as aniline, toluidine, and trichloraniline; and alicyclic amines such as 11-1-noramine and bornylamine.Also, urea , 1.3 dimethyl urea, 13-diethyl urea, 1.3-dipropylurea, etc., which can be readily prepared by heating or other means.
It is also possible to use compounds that generate amines. The amount of these imidized substances to be used varies depending on the degree of imidization and cannot be strictly limited, but is generally 1 to 250 parts by weight per 100 parts by weight of the methacrylic resin. If it is less than 1 part by weight, no obvious improvement in surface 4 thermal properties can be expected. Further, if the weight exceeds 250 feet, it is not preferable from the economic point of view. Among the imidizing agents used in the present invention, methylamine and ammonia are particularly preferred from the viewpoint of heat resistance and transparency. The "methacrylic resin" used in the present invention refers to a methacrylic acid ester homopolymer having an intrinsic viscosity of 0.01 to 3.0 or a copolymer with an ethylenic monomer copolymerizable with methacrylic acid varnish. polymer). Jl, Shinai i
J-functional polymers include methacrylic acid, acrylic acid ester, acrylic acid, methacrylic acid, sulphate,
L pa/, 2) Substitutions such as j runo, no sh/n, etc.
−n, etc. are reduced by 4. ! 'li German-Chinese merger +:, ', 1, bi'1.
For example, menol methacrylate, enal methacrylate,
Propyl ivy, methacrylate
ru, meccrylic acid isosol j, ivytacryl f'Wb・1
()-y-l, methacryl 11i-Q;, ri 1z...
-1-sil, norbornyl 7-notacrylate, methacryl M
2 1-Narusoy/ku・\-1-sil, methacrylic acid--sosil, examples of acrylic acid sprue include Eva, -Nacrylic jJd27Nal, acrylic acid sulfur,
Zo-11pyr acrylate, r1-butyl acrylate, 1'-sosotylacrylate, tert-butyl acrylate, mi-pacrylate, lyli'l-\xyl, norphonyl acrylate, 2-ethyl acrylate\nidocyl, acrylic You can use acid, alcohol, etc. In the method C of the present invention, methacrylic Methyl acid 11'L autopolymer or 2
7511i17j with 5% or more of methyl methacrylate
% or less copolymerizable ethylenic? A conjugation with the 11°1N isomer is preferred. In particular, a medium polymer of methyl methacrylate is most preferred from the viewpoint of transparency. The solvent used in the method of the present invention can be used without inhibiting the progress of the imidization reaction, which is a polymer side chain condensation reaction of the meth)lyl resin, and in the case of a partial imidization reaction, the solvent can be used for methyl methacrylate or methacrylate segment i. It must not be possible to make any changes in the ~ part. The solvent is a poor solvent with a boiling point of 50 to 135°C under normal pressure or one that can dissolve the methacrylic resin at room temperature, and a poor solvent with a boiling point of 135°C.
Use a mixed solvent with a good solvent that exceeds 260"C and that easily dissolves the methacrylic resin. Preferably, the poor solvent has a solubility of 1 + parameter δ value of 14.0 to 19
．． 5 (c:rlP/(:IlR) '''', and as a good solvent, the solubility pathometer δ value is 8.0 to 13.9 (ca 1./co?)''
' range (7J or i:+,) 1. Zl. 5:'t Example of refrigerant,'
-1-,'(4;l:) evening/-Luke; Alcohols such as 1-tutanol, 1-pentanol, and A-phtatonol, I8-tosylene',
Ethylhesi/Len, Cumen, Men-J-Len, ]-7
7 Tashi-n, U-I Nrin, Ethylhenzen, Noethyl \Sojdon, Pentyl \Nsen, Vinenylyarinon 1.4I group j;Korou water ÷, chemical lA1-14!7
January 1'! N, Isoho II, Tsuk11・-,=l
-, 1 nano, -7 tosol, dibu-nor on lille, no'\yasil: 1---- uru, -7 yusol,
hmm,;? , 1.-le, Bunarsoj-2~Le Cordel,
The horns of Schiffer Ether, Nokura Il, Noe 5'' Lengricorsi Kosenru Ether, etc. 1.:1--
Can you name some chill compounds? In this -) good solvent, -C is a very good solvent.
U7. 2 (Oh, the solubility parameter b for the present invention is Polymer Hunt Hook, 2nd edition, Seaflan Luso, 1
゛-co-1')-in-i'-kunt, /
``Noi Ri-n I''
Rin no, -I-': L -rl (
1'olymer 1landhook, 5econ
d times, , 1 °H+-; 1n11ru1+1i
, 11.1mmt:rl+ut, John Wile
y & 5on (, NCw York) (197
Groups listed in 5)

[1 (based on (9) (il'I
). The boiling point of the liquid in the mixed solvent used is 260° at normal pressure 1.
If it is higher than C, it becomes a garbage 1 reaction. It becomes difficult to separate and remove the solvent, components and volatile substances from the reaction product obtained in 1 minute. In addition, if the solubility parameter δ value of the poor solvent and good solvent in the mixed solvent used is 1:11, which is outside the range of 1-1, a homogeneous dust-1 reaction will occur, and the crystal t' Combining one car containing methacrylimide in i +'-> j
It's so bad. The mixed solvent 111 used in the method of the present invention is preferably used in a small amount from the viewpoint of productivity, but if the amount is too small, the effect of the solvent will be reduced. - LO (01 parts by weight is preferable. Also, the ratio of poor solvent to good solvent is 99/1 to 1/
99, preferably 90/10-10/9 (1 (weight ratio)
It is. The above-mentioned solvent used in the method of the present invention facilitates (<) the imidization reaction between the polymers of the methacrylic resin. This enables effective temperature control. As a result, a methacrylimide-containing polymer having excellent transparency and heat resistance as a desired optical material is obtained. The reaction temperature between the methacrylic resin and the imidized substance is 100° (: ~ 350° [:, preferably 150° C. to 300° C.) in the presence of a solvent.
If the reaction time is less than 35F, the imitation reaction will be slow, and if it exceeds 35F, the decomposition reaction of the raw material methacrylic resin will easily occur.The reaction time is not particularly limited, but from the viewpoint of productivity, the shorter the better; - In the six imidization reactions, if water is present in the reaction system, the ester moiety of the methacrylic resin will undergo water Q/hydrolysis as a side reaction during the imidization condensation reaction process, and as a result,
Methacrylic acid is produced in the resulting methacrylic acid-containing polymer, making it difficult to obtain a methacrylic acid-containing polymer having the desired amount of imilization, which is the object of the present invention. Therefore, this reaction is carried out under conditions where the reaction system does not substantially contain water, ie, where the water content is 1% by weight or less, preferably under anhydrous conditions. In addition, the atmosphere of the reaction system is nitrogen, -IJ? ),
It is preferable to carry out the reaction in an inert gas atmosphere containing argon gas or the like. The amount of imidization of methacrylic resin in the method of the present invention is
From the point of view of heat resistance, the structural unit represented by the general formula (II) is 2.
The amount is in the range of 100% by weight, preferably 30 to 100% by weight, and more preferably 50 to 100% by weight. The methacrylimide-containing polymer obtained by imidization by the method of the present invention has an intrinsic tenacity (the measurement method will be described later) of 0.0
2 to 4.5. The reactor 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 reactor, a screw extrusion type reactor, a column reactor, a tube wall reactor, etc. A reactor, a duct-like reactor, a tank wall reactor, etc. are used. In order to perform imidization uniformly and obtain a homogeneous -ZC method ([1) tacrylimito-containing polymer, the supply "-1
In addition, it is preferable to use a tank wall reaction device equipped with a stirring device such as 1 and 1-1, which has a mixing function throughout the reactor. Polymer Condensation Reaction) 1: Separating and removing most of the volatile substances from the reaction product containing the components. The remaining volatile substances in the final polymer are separated and removed so that the content thereof is 2% by weight or less, preferably 1% by weight or less. Removal of volatile substances can be carried out using a conventional Ghent extruder, deporatizer, etc., or by other methods, for example, diluting the reaction product with a solvent and injecting it into a large amount of non-IJ solvent medium. Precipitation, drying, etc. can be used. In the method of the present invention, an antioxidant,
Additives such as plasticizers, lubricants, and ultraviolet absorbers can be added. 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 solvent is taken from the solvent storage tank 1 through the filter 33 and transferred to the solvent supply tank 4.
sent to. Additives added as needed are supplied from the storage tank 5 to the solvent supply tank 14 via line 6 and dissolved therein, passed through line 2, and then transferred to resin dissolution tank 10 via line 7 by pump 3. 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 IO is equipped with an agitator 11 and a jacket 12, and a heat medium flows into the jacket 12 through openings 13 and 14. The melted resin in the resin dissolution tank 10 passes through a discharge line 15, a pump 16, and a line 17, and then flows into the reaction tank 20.
The imidized material is sent from the imidized material storage tank 18 through the line 19 to the filter 34, and the imidized material is supplied to the reaction tank 2.
Reacts in 0. The reaction tank 20 is equipped with a spiral ribbon stirrer 21 and a jacket 22, into which a heating medium flows through openings 23 and 24. The reaction product in the reaction tank 20 is discharged through a discharge line 25 and a pump (
1)) 2G is sent to the volatile matter separator 28 through 2
．． Volatile storage 1; j (machine 2B is tsuku', I J-, E (
), -・nt; (1. Equipped with f stage 32 for heating. [Effect of the invention] If J is added to the L method of the present invention described below, the imidation reaction can be easily carried out. It is possible to produce methacrylate, I-containing car combinations with low quality and advantageous L'Y (L'Y) advantageous production of methacrylic and I-containing car combinations with low quality (0, 1 and 1 in transparency and heat resistance). In particular, the light transmission performance of the obtained polymer is
At 6 nm, it is 5.000 dB/kn11J-'. , fluorescent tube filter, liquid crystal filter,
Meters, digital display boards, etc.) - display related, lighting optical related, automobiles, etc. / Nodorite covers, cabinets, electrical parts, brushing / filter molding materials with other resins, etc. It can be used in a wide range of applications, and its commercial, ON, and value are extremely high. [Examples] Hereinafter, the present invention will be further revised and explained with reference to Examples. All parts and percentages used in the examples are by weight. In addition, the apparatus shown in FIG. 1 used in the examples? 1' series C1 [This specifies the following specifications. Resin dissolving tank 500! Reaction tank 40n Volatile separator shaft screw: - Extruder screw: 30n1mφx 720+n+nR: Gent manager: 50 nun In these Examples, the hesitivity of the polymer was measured by the following method. (1) The infrared absorption spectrum was measured by the KBr disk method using an infrared spectrophotometer (model 285 manufactured by Hitachi, Ltd.). (2) The intrinsic viscosity of the polymer is
eereax-Bischof f) Using a viscometer, measure the flow time (L ! ; ) of a dimethylpornamide 78 solution with a sample polymer concentration of 0.5% by weight and the flow time (L ! ; ) of cymenalformamide 1 il A degree. 2510.
Io [measured in two, E! ;/L(l Determine the relative viscosity ηrel of the polymer from the clay, then use the following formula.
In the formula, (: L; l represents the number of grams of polymer per 100 m9 of refrigerant.) (3) Heat distortion temperature number jl: AS1'Mll 648
1. (Measured accordingly.) (4) The melt index of the polymer is 8 STMD.
1238 (230°; g number for 10 minutes at a load of 3.8 kg). (5) Measurement of monoimidization II+ (%) of the polymer is performed using the elemental content)
MT 3) Nitrogen content and concentration at 1 ton NMRJNM FXlo () (JEOI)
Spectrometer l (measured by lOMIIz7)
is. ((i) ij) The light-transmitting performance of the polymer was measured by preparing a measurement sample according to method C of Icho. Fig.2
5. Use a screw-in type extruder consisting of a piston 46 with an outer diameter of 38 mmφ and a nozzle 47 with an inner diameter of 31 mmφ U7
The barrel temperature of the extruder was increased with a heater 4 and adjusted to 220-250°C±1°C. Then, in the barrel 45, a polymer sample 49 that has been dried for 1 minute is placed.
and melt it, constant speed motor 5Gc = piston 4
6, extrude the molten polymer in the form of a strand from the nozzle 47, and take it up with the lower two pumps 50.
A S1-run Fc with a diameter of 1 mm was formed. In the process of picking up this shaped 1 Pengφ SuI Lan 1,
Low refractive index polymer (2,2,2 to IJ fluoroethyl methacrylate polymer, j (< Fd average molecule! 8X10
', refractive index n, 'J, 410) dissolved in ethyl acetate (polymer concentration 35% by weight) is passed through the impinging bot 51 and applied to the surface of the shaped strand.
A coating film with a thickness of 5 mm (dry thickness) was formed. The shaped strand 1 having this coating film is passed through a heat exchanger 52.
Air 53 heated to 50°C was circulated (1[Ir
/) 71 in) The ethyl acetate container was removed in the dryer 541-16 through 7, and the photoconverter having a diameter of monovalent φ was wound up in the winder 55. This obtained optical transmitter was used as a sample for measuring the light transmission performance. Next, using this sample, the light transmission performance (light transmission performance) was evaluated using the apparatus shown in FIG. FIG. 3 is a schematic diagram of a device for adjusting the light transmittance of a sample by ff1l + -4, in which light emitted from a Haloken lamp 62 stabilized at -2 by a stabilized power supply 61 is passed through a lens 63 to -C.
After collimating the beam, it is made monochromatic by the T beam filter 64, and an open 1-'I number equal to 0 can also be seen at the focal point of 7.1. , the incident end surface 66 of the optical transmitter sample 0 ( ) is at the position r
Adjust G so that it is 7, and let the light enter the transmitter sample 60. From the incident end surface (8()) to the end of η/IU7, the light is attenuated and emitted from the emitter 67.
At 168, Y is converted to a current, and amplified by an amplifier 69 of the current/voltage variation model to obtain a voltage of 1. First, cut the optical transmission body 60 to a length of 1. Cut the sea urchin drawing: I: +5 side perpendicular to the strand axis, and cut it into a smooth surface using the above-mentioned device (Fig. 3). Be sure to install the entrance end surface 60 and the 11" exit end surface 67 so that they do not move during measurement. Read the reading on the voltmeter in a dark room. Set this electric Li value to 1.Next, turn on the indoor furnace. , output end surface 67
is removed from the apparatus, and the optical transmission body 60 is cut off from this end face at a point 71 of length p. Then, the end face of the power light transmitting member attached to the device is set to a plane perpendicular to the strand axis, as it was at the beginning, and this is used as a new output end face to be attached to the device. During these operations, care must be taken not to move the incident end surface l6 in order to keep the amount of incident light constant. Return to the dark room and read the reading on the voltmeter at step 1. shall be. Optical transmission loss (α) is calculated by d1 using the following formula. (1!) Here゛(, p; IQ of optical transmission body (km) 1,, +2
, light amount (voltmeter reading value) The measurement strip A'1 in the present invention is as follows. 1-Winter filter (main wavelength) 64 Gnmro (total length of optical transmission body) 210 (or 5 m) p, (cutting length of optical transmission body) 1.5 m (or 4.5 m) r (1 of bobbin)
White ゛1 child) 19 (1 turn mouth iron, bobbin is used to J the device in one!) Person ◇: 9 and the distance between 66 and the output end face 67 3 (1 (approximately +n) U7 to become
, the remaining optical transmission body is wound around a bobbin (not shown). It is possible to change the dominant wavelength of the interference filter from 400 nm to 1200 nm (51).The measurement of the open 1J number of the optical transmission body was carried out using the measuring device shown in Fig. 4. This is a collimated light source with a built-in Bahal, 1 gen lamp.The output light of the light source is converted into a heart wave 1...
(In 5 (l n In, ゛l′ clay width; 3110+0-)
Eye j1no. The parallel light rays are passed through the router 82 (after being made monochromatic, the number is that of the optical transmission body, [, Rimo), and the parallel rays are focused by the sharp lens 83 and focused on one end surface 85 of the optical transmission body 84. Sa-lro. The end face 85 is cut perpendicular to the strand axis of the optical transmission body, finished smooth, and fixed to a fixture 86 so that the J, S, S, and i axis and the optical axis 87 are aligned. The incident light passes through a light transmission body having a total length l, and then exits from the end face 88 of the force. Fix the fixed shaft 81) with a fixture 90 so that the end surface 338 finished with a smooth surface at an angle with the strand axis is aligned with the center axis of the fixed shaft 3C), and the Sumilan 1-axis and +1il center axis are perpendicular to each other. Fixed to. 91 rotates around the central axis of the fixed shaft 89 with a rotating arm;
This can be done by reading the rotation angle θ. 92 is a photomultiplier tube that detects light; /. - The amount of light that enters the hole 93 and passes through the hole 94 is measured as a current. The hole 94 has a diameter of 1.5 mm.
It is located on the A3 device 125 mm from the central axis. Using the apparatus configured as shown in Fig. 3, the emitted light is measured by the relationship between the rotation angle θ of the rotary arm and the current in the photoelectron multiplier layer. 1. 'r LJ becomes. If the maximum current is 1□, find the opening 1-] number (NA) from the angle width 2θW that decreases to 10, force /2 and the following formula, 1
I can turn it on. N p −”−: i ! nθW (7) The remaining volatile matter is 20 + 1 'C2331111
1111g of reduced pressure heating type dry heat ・Power of ζ polymer in the vessel 11
′! ,)t'(7 friends j(?H(II'+4, then 1'Q is calculated in the following formula,]). WO WO is h: in the polymer of the initial iUl. W is Example 1 1 minute I:'l t%: Sifted Nuccryl 11 polymethyl acrylic acid Menal co-neutral coalesce (IFC!it, l
:L・-(] !1/l, hardness j viscosity (1,51
) 100 copiest: ,, 4j:if' meat de n d 71
L'-c water 7, Cal chloride, pano 1. I-C
After drying and collecting the stems, 0.1μm1 (Soluo IJ bottle)
(Produced by l(1)) - (790 parts of filtration L7 + SO L; J:; J, after dehydration and drying, 0
1 μIll Fluo L2 bore (iJli: ii5 L,
10 parts of methanol. I'l'
l' + R';1.1') τ19 Preparation) Mulberry
. Next, this solution was continuously fed to the C reaction tank at a feed rate of 5 kg/n, li, and stirred at a rotation speed of 90 rpm.
m, temperature at 230°C, section II. Then, add 0.1μIll of dried methylamine to iI in a full 11th bore.
20 mol/11. JHII reacts at a rate between '1
Continuously supplied into the H, the internal pressure is 55 kg/afi・
U7 was in G. The temperature in the reaction tank was 230° [: Otsuko U7, and the average residence time in the reaction tank was 3.0 hours. Mix the reactants
The solvent was continuously fed to a Jllll extractor to separate and remove the volatile substances that make up the solvent. - The temperature of the extruder was set to 230°C in the extrusion section, 230°C in the extrusion section, and a vacuum level of 9 mm11B in the extrusion section.Abs. A pellet-shaped polymer having good transparency was obtained by cutting the strand extruded from the die. - Volatile components ejected from the Ghent section by υ1 were cooled and collected. When the infrared absorption spectrum of the obtained polymer was measured, the wave numbers were 1720c+n-', 1663cm', and 7.
50 tIll contains methacrylimide 1 city combination 1,
J) C. ) was lost. Also, nuclear magnetic co-I! r5
A signal indicating the structure of the spectrum was shown. As a result of elemental analysis, the nitrogen content was 8.3%, and it was confirmed that it was an almost completely N-methylated methacrylic potato 1114 combination. When the polymer 1 (1) was evaluated, it showed the following 1, L. Melt index 1.75g/10min Heat distortion temperature 17) ('C residual volatile content
0.35 part book [1 sentence combination PE L 71. Translucent +? An optical transmission body was prepared using the apparatus (31. When measured using the equipment shown in Figure 3 and Figure 4, it was approximately 650 dll/km.Also, the l?tlCl number of this optical transmission body was 0.58. 1'' number (+I' is N
, calculated assuming that the refractive index of the 2-l refluorinated noethyl methacrylate polymer is 1.410 Salero F'l:
g life (direct (NA"-vrII +-2"rlP"
” 0.59). Examples 2 to 6 Various methods were used as in Example 1 except that the methacrylic resin, imidizing agent, and reaction conditions were used (not shown in Table 1). A methacrylimide-containing polymer was obtained. The internal pressure of the reaction tank was set to 20 to 80 kg/CIM. The properties of the obtained polymer are shown in Table 1. After drying for 1 minute in a 10N reactor equipped with a 2g sample and a 1-heater, the mixture of methacrylic acid and methacrylic acid (intrinsic viscosity:
0. ! i5) Add a mixture of 0 parts of H), 80 parts of toshishin, and 20 parts of methanol, which had been treated in the same manner as in Example 1, and after purging with nitrogen for 1 minute, stir at 230"C and heat the polymer. ) and 7. Next, add 18.6 parts of C1230' (0, fi
Shiruhi)? 8th angle q L, Nogo 1 chaos dry Tsutanoru? 8
Filter 1-1 and add the d woman to the internal pressure 5 (i kg/
The reaction was carried out at +11110 for 3.0 hours. After the reaction was completed, the N-nonalmethacrylic-1-amide-containing polymer solution was taken out, and the solvent was removed and dried in a vacuum dryer at 150° to obtain a porous polymer. When the infrared absorption spectrum of the obtained polymer was measured, the wave number was 1720 cm, 1.16 ('i3 cm-' and 7
At 50 cm, an absorption characteristic of the methacrylimide-containing autopolymer was observed. The evaluation results of the polymer are shown in Table 2. Examples 8 and 9, Comparative Examples 1 to 6 Various polymers were produced by repeating the method of Example 7 under the conditions shown in Table 2, and evaluated. Comparative Example 7 After thoroughly drying the same methyl methacrylate copolymer used in Example 1, it was supplied at a rate of 12 kg/11r to a twin screw extruder (L/D-33) with a screen diameter of 50 mmφ. . This twin-screw extruder is composed of a pellet plasticization zone, an imidization agent supply zone, an imidization reaction zone, a Ghent zone, a metal ring extrusion zone, and a die section, and the respective temperatures are 245 °C, 255 °C, 2
The temperatures were set at 75°C, 270'C, 215'C and 255°C. The degree of vacuum in the hent zone is 5 mm 11 g a
maintained at bs. - A check valve was connected to the imidizing agent supply zone of the shaft extruder, and methylamine was supplied at a rate of 2.79 kg/hour. The strand obtained from the die part was cooled with water and then pelletized to be used as a sample. After drying this sample, it was shaped into a strand using an extrusion shaping device and evaluated for light transmission performance in the same manner as in Example 1. When the infrared absorption spectrum of the obtained polymer was measured, the wave numbers were 1720 cm-', 166.3 cm-' and 75 cm-'.
Absorption peculiar to polymers of N-methyl methacrylimide was observed at 0 cm, and it was confirmed that it was a combination of methacrylimide 811. The physical properties of the obtained 11'c coalescence were evaluated. The results are shown below. Mel 1-index 8.5gr/10min Heat deformation temperature 153°C Light transmission performance 35000dB/km (
646 nm), it was found that even if the imide coating reaction was carried out in a solvent-free system, a -(mi)-containing polymer with excellent light-transmitting performance could not be obtained. The reason for this is that if there is no solvent in the extruder, the high-purity molten methacrylic polymer and methylamine will not be mixed at the same time, and the reaction will not proceed uniformly. Conceivable.

[Brief explanation of the drawing]

FIG. 1 diagrammatically shows one embodiment of the apparatus used in the practice of the invention. 1... Solvent storage tank, 4... Solvent supply tank, 8
...Resin pellet storage tank, 10...Resin dissolution tank,
18... Imidization substance storage tank, 20... Imidization reaction tank, 28... Volatile separator. FIG. 2 is a schematic diagram of an apparatus for preparing a sample for measuring the light-transmitting performance of a polymer. FIG. 3 is a schematic diagram of a device for measuring the light transmission performance of a polymer sample. FIG. 4 is a schematic diagram of an apparatus for measuring the numerical aperture of a polymer sample. FIG. 5 is a diagram showing an example of the results measured by the apparatus shown in FIG. 4.

Claims (1)

[Claims] 1) Methacrylic resin and general formula R-NH_2(I) (wherein R is a hydrogen atom or an aliphatic group having 1 to 20 carbon atoms,
(representing an aromatic or alicyclic hydrocarbon group), a poor solvent with a boiling point under normal pressure of 50 to 135°C and which is difficult to dissolve the methacrylic resin at room temperature, and a poor solvent with a boiling point under normal pressure of 50 to 135°C In the presence of a mixed solvent with a good solvent that is higher than 135°C and lower than 260°C and easily dissolves the methacrylic resin, 1
General (II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula, which is characterized by reacting at a temperature of 00°C to 350°C and then separating and removing volatile substances from the resulting reaction product. (II) Excellent transparency and heat resistance, consisting of 0-98% by weight of structural units derived from 2-100% by weight of the structural unit represented by the formula (wherein R is as described above) derived from an ethylenic monomer. A method for producing a methacrylimide-containing polymer.