JPS58134104A - Continuous polymerization - Google Patents

Abstract

PURPOSE:A couple of endlessly moving bands are arranged so that one band comes on the other to seal the space between these two bands and the polymerization of methyl methacrylate or the like is conducted in the presence of a polymerization initiator in the hot water polymerization zone at specific conditions to produce sheet polymer of high quality in low costs. CONSTITUTION:A couple of endlessly moving bands 1 and 2 are arranged in an upper and lower position, given a tension with pulleys 3-6 respectively and run in the same direction at a same speed. A couple of continuous gaskets are brought into contact with the both bands on both sides respectively to seal the space betwen the moving bands and a composition consisting of a syrup of methyl methacrylate with a polymerization rate of 15-35wt% as the major component and of (monoalkyl)cumylperoxy neodecanoate as a polymerization initiator is continuously fed into the space. Then, they are passed through the hot water polymerization zones A-F to effect polymerization. At this time, polymerization is carried out under such conditions as the relationship between the mole number of the polymerization initiator per 100pts.wt. of the strup and the temperature in the polymerization zone is in the area surrounded with points A, B, C and D.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a polymerization rate of 1 containing methyl methacrylate as a main component.
A polymerizable liquid composition in which a polymerization initiator, cumyl peroxyneodecanoate or/and monoalkyl cumyl peroxyneodecanoate, is dissolved in 5 to 85% by weight of silica is continuously poured into the space between the moving bands. The present invention relates to a method for continuously producing plate-shaped polymers of methacrylic resin by supplying and polymerizing methacrylic resin.

Generally, a cell casting method using two sheets of tempered glass is known as a method for producing a plate-like polymer of methacrylic resin with excellent transparency, gloss, and weather resistance from methifre methacrylate. However, this method requires batch operations such as cell assembly, liquid injection, and frame disassembly, and is mostly manual, requiring a lot of manpower and high manufacturing costs, so rationalization was considered.
A continuous casting method has been developed to replace the cell casting method and is being industrialized.

As a continuous casting method, for example, U.S. Patent No. 260
Publication No. 0728, Japanese Patent Publication No. 46-41602, No. 4
As shown in Publications No. 9-85818 and No. 49-86944, a polymerizable compound consisting of methyl methacrylate and a polymerization initiator is injected between two endless bands located above and below to form a band. Along with the movement,
A method is known in which the polymerization of methyl methacrylate is completed by first carrying out main polymerization using a hot water bath, followed by heat treatment using hot air or a far infrared heater, and then taking out a plate-shaped polymer from the other end. However, the continuous casting method requires high equipment costs and increases the manufacturing cost of methacrylic ml plates, so production that polymerizes in a short time and highly efficient polymerization technology are required. On the other hand, generally, the time on the stand is shortened (this results in disadvantages such as foaming of the resin plate during polymerization, foaming when heated for processing, and poor solvent resistance. Even when the thickness of the polymer is 8 m+ or less, the total polymerization time required for main polymerization and heat treatment time is as described in Japanese Patent Publication No. 48-16718, No. 4
As known from 8-16998 and 48-16994, it was not possible to reduce the time to 80 to 60 minutes.

The present invention provides a method for producing plate-shaped polymers with low production cost and excellent quality by continuous casting method. A polymerizable liquid composition prepared by dissolving a polymerization initiator, methacrylic peroxynedecanoate or/and monoalkyl cumyl peroxynedecanoate, is supplied to the space between the moving bands and polymerized. This method is characterized by the continuous and efficient production of lactic acid plate-like polymers.

Further, in the present invention, when the thickness of the plate-like polymer to be produced is 8fi or less, the main polymerization time is within 20 minutes, when the thickness is larger than 8a and 4- or less, the main polymerization time is within 25 minutes, and when the thickness is thicker than 4a+, it is within 25 minutes. 61111 or less, it is possible to shorten the main polymerization time to within 80 minutes, and furthermore, it is possible to reduce the residual overlapping percentage to 1.5% or less in a short heat treatment time.

In order to efficiently produce a plate-like polymer of methacrylic resin by the 4M casting method and to achieve marketable and excellent quality, it is preferable that the following five conditions be satisfied.

(11) When the thickness of the plate-like polymer to be produced is particularly 8W or less, the main polymerization time is within 20 minutes, preferably within 15 minutes.

(2) No air bubbles are generated in the plate-shaped polymer during main polymerization or heat treatment, that is, there is no polymerization foaming in the produced plate-shaped polymer.

(8) Residual seven-point wrinkles in the produced plate-like polymer are 1.
6% or less, that is, the plate-shaped polymer has a low heat deformation temperature.

(4) Possible to bond with solvent and have excellent solvent resistance.

(5) No bubbles are generated when the produced plate-shaped polymer is heated at 180° C. for 80 minutes, that is, no foaming occurs due to heating.

Regarding point (1), since continuous cast polymerization equipment requires a large investment in equipment, it is an essential condition to improve production efficiency.

Furthermore, regarding point (2), the presence of air bubbles in the produced plate-shaped polymer significantly impairs the commercial value of the methacrylic resin, and these air bubbles are present during the main polymerization or heat treatment. Therefore, it is necessary to appropriately select the main polymerization conditions. (Also, regarding the point (8), it is not preferable that the amount of residual additives in the produced plate-shaped polymer exceeds 1.5% by weight, since the heat distortion temperature will decrease and the creep properties will deteriorate. For this residual monomer filter, it is necessary to appropriately select the heat treatment conditions along with the main polymerization conditions, and it goes without saying that the heat treatment time also affects the production capacity of plate-like polymers, so it is preferable to keep it as short as possible. .

Regarding the point (4), it is necessary that solvent bonding is possible since adhesive processing is often carried out using a solvent such as dichloromethane in the produced plate-like polymer of methacrylic resin.

At the same time, it is necessary to have excellent solvent resistance, since crazing due to solvent resistance will impair commercial value.

Regarding point (5), plate-shaped polymers of methacrylic resin are usually heated and processed by bending or vacuum forming, but at this time, if the temperature at which the plate-shaped polymer starts to heat and foam is low, the heating process may be too low. It must be ensured that foaming does not occur when the plate-shaped polymer is heated at 180° C. for 80 minutes, since bubbles will form and the product will lose its commercial value.

The above-mentioned six conditions are essential for efficiently producing a plate-like polymer of methacrylic resin of excellent quality by continuous casting (ffl), and these five conditions must be satisfied at the same time.

In order to simultaneously satisfy the five conditions mentioned above, the present inventors used a polymerization initiator such as 2,2'-azobis(2,4-dimethylvaleronitrile) (hereinafter referred to as Using ADVN) and lauroyl peroxide (hereinafter referred to as LPO), polymerization was carried out under various conditions to obtain a plate-like polymer with a thickness of 81 W or less, and the main polymerization time was 80 to 40 mm. If you lengthen it to minutes, then (2) above.

(81, It was possible to satisfy only the conditions (4) and (5) at the same time. However, when the thickness of the plate-like polymer is 8W or less using ADVN or Ll'O, the above ( In order to keep the main polymerization time within 20 minutes, preferably within 15 minutes, ADVN and L
If the amount of PO used is increased, polymerization foaming may occur in the obtained plate-like polymer, or foaming may occur at a temperature lower than 180°C, resulting in a plate-like polymer of satisfactory quality. However, even if we tried to shorten the main polymerization time by changing the temperature of the hot water bundling zone without increasing the amount of ADVN or LPO used, polymerization foaming would occur in the resulting plate-shaped polymer. It was found that it was not possible to obtain a satisfactory plate-shaped polymer. This means that using the polymerization initiator ADVNJPLPO, which is used in the visual continuous casting method, it is impossible to satisfy the above six conditions at the same time. This indicates that it is impossible to obtain a plate-like polymer of a certain trivial quality.

The present invention provides a continuous polymerization method that simultaneously satisfies one of the conditions for 51-F described above.

That is, in particular, the present invention uses a specific range of usage amounts of cumyl peroxyneodecanoate or/and monoalkyl cumyl peroxyneodecanoate as a polymerization initiator, and a specific main polymerization temperature range and heat treatment temperature. By polymerizing silica containing methyl methacrylate as a main component and having a polymerization rate of 16 to 86% by weight under conditions within a range,
We have discovered a method for continuously producing a plate-shaped polymer of methacrylic resin that satisfies the above six conditions at the same time, and when the thickness of the plate-shaped polymer finally obtained as a funeral product is 8H or less. It is possible to set the main polymerization time within 20 minutes or even within 16 minutes, and when the thickness is larger than 8Im and 4a or less, it is within 25 minutes, and when it is larger than 4m and 6- or less, it is within 80 minutes. Is possible.

In addition, the main polymerization time is shortened due to the misfire, and the main polymerization time is shortened by 1:1 compared to the time using ADVN or LPO, and the specific main polymerization temperature range and heat treatment temperature range of the present invention By polymerizing with
Less than % by weight - it is possible to rub, the quality of the obtained plate-shaped polymer is also polymer foaming, the heat distortion temperature is high,
It can be accessed by solvents and has excellent solvent resistance.
Many effects were discovered, such as no foaming even after heating at 80°C for 80 minutes, making it possible to further improve production efficiency.

In the present invention, the sillage containing methyl methacrylate as a main component supplied to the space between the moving bands has a polymerization rate of 15 to 86% by weight, preferably 20 to 80% by weight,
The viscosity of the sillage is preferably 5 voids or more at 26°C. Polymerization rate of Shirabu is 15゛ Electricity%
When the amount is less, the production efficiency of the plate-shaped polymer becomes faster. For example, when the thickness of the plate-shaped polymer is less than 8, the main polymerization time is 2.
It has become difficult to produce plate-shaped polymers of methacrylic resin of excellent quality within 0 minutes, and even more so since the main polymerization time is 1 minute.
It is impossible to do it within 6 minutes.

On the other hand, when the polymerization rate of the syrup is more than 85% by weight, the viscosity of the syrup increases, making it difficult to supply the syrup to the space between the moving bands, which is not preferable. The viscosity of the shirub is preferably 6 poise or more at 25°C. If the viscosity is 6 poise or less, foaming is likely to occur during polymerization when the main polymerization time is shortened, and the quality of the produced plate-shaped polymer, especially heat foaming. The temperature at which this occurs tends to be low. On the other hand, as syrup viscosity increases, it becomes difficult to supply syrup to the space between the moving bands, so the upper limit of syrup viscosity is usually up to 100 poise.

That is, the silub has a polymerization rate of 15 to 85%, and a polymerization rate of 26%.
It is preferable to use one having a viscosity of 5 to 100 poise at °C.

The main component of methyl methacrylate used in the present invention is methacrylic acid alkyl ester (however, the alkyl group has 2 to 8 carbon atoms), styrene, etc., if the amount is 80% by weight or less based on the total weight of the silica. and halogen-substituted or alkyl-substituted derivatives thereof, vinyl acetate, acrylonitrile or its derivatives, acrylic acid alkyl esters (provided that the alkyl group has 1 to 8 carbon atoms), and the like. In particular, an acrylic acid alkyl ester is effectively used to raise the temperature at which heating and foaming begins when the main polymerization time is shortened. Examples of acrylic acid alkyl esters in which the alkyl group has 1 to 8 carbon atoms include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, inbutyl acrylate, 5ec-butyl acrylate, te
At least one selected from rt-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, and octyl polyarylate is used, particularly methyl acrylate and ethyl acrylate.
゛・Acrylate is preferred.

The amount of acrylic acid alkyl ester used is in the range of 0.6 to 15% by weight based on the total weight of the silica. When the amount of the acrylic acid alkyl ester is less than 0.5% by weight, no effect of increasing the temperature at which the obtained plate-like polymer starts to heat and foam will not appear. Further, as the amount exceeds 15%, the thermal deformation temperature of the plate-shaped polymer decreases and the solvent resistance decreases, which is not preferable.

Furthermore, it has been surprisingly found that by containing an acrylic acid alkyl ester, it is possible to reduce the amount of residual monomer in the plate-shaped polymer to 1.5% by weight or less with a shorter heat treatment time.

In addition, in the present invention ζ, heat stabilizers, ultraviolet absorbers, colorants, plasticizers, mold release agents, and various fillers may be added to the above-mentioned syrup as necessary, as long as the amounts are within the range that achieves the purpose of the present invention. It may also be used by containing.

Polymerization rate of 1 based on methyl methacrylate of the present invention
In order to prepare a sillage with a concentration of 6 to 5% by weight, methyl methacrylate or a mixture containing methyl methacrylate and a monomer copolymerizable with the methyl methacrylate and/or the additives and fillers mentioned above are partially polymerized to give a predetermined amount. After partially polymerizing methyl methacrylate or the mixture, monomers copolymerizable with the methyl methacrylate and/or the additives and fillers are added to achieve a predetermined polymerization rate and composition. or the monomers and/or the additives that can be copolymerized with methyl methacrylate or methyl methacrylate, and the electropolymer obtained by polymerizing these monomers or mixtures;
Methyl methacrylate ink containing a filler is dissolved to achieve a predetermined polymerization rate and composition.

Examples of cumyl peroxyne, odecanoate and/or monoalkyl cumyl peroxynedecanoate which are the polymerization initiators of the present invention include cumyl peroxy neodecanoate, iso4propyl cumyl peroxy neodecanoate, N-butylcumyl peroxyneodecanoate, inbutylcumylperoxyneodecanoate, 5CC-butylcumylperoxyneodecanoate, tertiary-butylcumylperoxyneodecanoate, 2-ethylhexylcumyl One type or two or more types selected from peroxyneodecanoate, ethoxycumyl peroxyneodecanoate, 8-methoxybutylcumyl peroxyneodecanoate, etc. can be used in combination. Furthermore, if the weight is 10 times or less of the amount of cumyl peroxy neodecanoate or/and heptanoalkyl cumyl peroxy neodecanoate used in the present invention, handling, work safety, etc. For this purpose, plasticizers that do not easily react with the polymerization initiator of the present invention such as dibutyl phthalate and dioctyl phthalate, and diluents that do not easily react with the polymerization initiator of the present invention such as mineral spirits and toluene are used. It can be used together with the polymerization initiator in the invention.

The amount of cumyl peroxyneodecanoate and/or monoalkyl cumyl peroxynedecanoate used as the polymerization initiator of the present invention is as follows:
What is the relationship between the molar parts of cumyl peroxy neodecanoate and/or monoalkyl cumyl peroxy neodecanoate relative to the it part and the temperature (C) of the hydrothermal polymerization zone? Letter points A (IX1790) and B (IXl
o-", 85), C(8X10"lI, 60), D(l
By selecting the temperature of the hydrothermal polymerization zone together with the amount of the polymerization initiator of the present invention so as to be included in the closure region formed by connecting each point of It is possible to self-sufficiently produce plate-like polymers.

Generally speaking, as the thickness of the plate-shaped polymer product finally obtained increases, polymerization foaming is more likely to occur due to the generation of polymerization heat. 11, and conditions in which the temperature in the hydrothermal polymerization zone is low are preferred. Conversely, this means that the smaller the stiffness of the plate-like polymer obtained as the final No. It represents °.

The final result is obtained from the above. Among the conditions limited within the closure region of FIG. 1 depending on the thickness of the plate-like polymer, the following conditions are preferable.

(1) When the thickness of the final plate-shaped polymer is 8 or less, trielectric oxide neodecanoate or/and monoalkyl cumyl peroxyneodecanoate or monoalkyl cumyl peroxyneodecanoate or The relationship between the molar parts of decanoate and the temperature C) of the hydrothermal polymerization zone is shown at point A tl in Figure 2.
xlo-', 90), BIIXIO-'', 85) 1.C
(8XlG", 6"0), D (8X1G-', 70)
It is preferable that the condition is included in a closed region range formed by connecting each point of with a straight line.

,・1:.

(2) When the final number and the thickness of the plate-like polymer 1.1 obtained as a product are thicker than 8 g (4 m+ or less, cumyl peroxyneodecanoate or/and The relationship between the molar parts of monoalkyl cumyl peroxyneodecanoate and the temperature in the hydrothermal polymerization zone is shown at points A (IXIO'', 90) and B on the $8 diagram.
(lXl0-2.80), c (B x t o-2,
60), D(2X1G-', 66) are preferably included in a closed region range formed by connecting each point with a straight line.

(8) When the thickness of the plate-shaped polymer finally obtained as a product is thicker than 44 but not more than 611, cumyl peroxyneodecanoate or/and monoalkyl cumyl per 100 parts by weight of the sillage of the present invention is used. The relationship between the molar parts of luperoxyneodecanoate and the temperature (C1) of the hydrothermal polymerization zone is shown in Figure 4 at points A (IXIO-4,90) and B (7×
. 10-”, 80), ctaxto-*, 60), D(
IXIO-', 65) is preferably included in a closed region range formed by connecting each point with a straight line.

The straight line AB in Figures 1 to 4 of the present invention indicates the upper limit of the temperature of the hot water polymerization zone in polymerization foaming for the polymerization initiator in the present invention, and the straight line BC indicates the temperature of the plate-like polymer obtained as a product at 180°C. The boundary of the upper limit value of the polymerization initiator that can be used in the present invention for thermal foaming when heated for 80 minutes at
The straight line CD represents the boundary of the lower limit of the temperature of the hot water polymerization zone with respect to the amount of polymerization initiator used in the present invention so that the main polymerization time to obtain a plate-shaped polymer is within the target time.
A represents the lower limit of the amount of the polymerization initiator to be used in the present invention in order to reduce the amount of residual upper layer in the plate-like polymer product to 1.5% by weight or less.

Straight lines AB and BC1C in FIGS. 1 to 4 of the present invention
D.

DA forms a closed region of the relationship between the amount of polymerization initiator used and the temperature of the hydrothermal polymerization zone in the present invention, and if the conditions are within this closed region, polymerization can be carried out using the silica of the present invention. By doing so, it is possible to easily obtain a plate-shaped polymer that simultaneously satisfies the five conditions mentioned above. Note that the caps of cumyl peroxy neodecanoate and monoalkyl cumyl peroxy neodecanoate in FIGS. 1 to 4 of the present invention are expressed on a logarithmic scale.

Furthermore, using the silica tube of the present invention, the relationship between the amount of the polymerization initiator of the present invention used and the temperature of the hydrothermal polymerization zone was conducted within the closed region shown in Fig. 1, and then heat treatment was performed at 110 to 150°C. When carried out at high temperature, the amount of residual upper layer in the plate-shaped polymer decreases to 1.5% or less in a very short period of time, resulting in plate-shaped polymerization with a low heat distortion temperature and excellent solvent resistance. can get things. .

In addition to the polymerization initiator of the present invention, other polymerization agents may be used as necessary, as long as the temperature at which heating and foaming begins in the plate-shaped polymer finally obtained in the present invention is lower than 180°C (but not within the range). An initiator may also be used in combination, for example lauroyl peroxide or tert-butyl peroxypivalate.

The manufacturing device used in the present invention is generally known as a double band conveyor, in which two consecutive moving bands in a vertical positional relationship are made to travel in the same two directions at 11 speeds, and both sides of the moving bands are Each evening, at least one continuous gasket is run in contact with the self-moving bands to seal the space between the moving bands, and the polymerizable liquid composition is continuously supplied into the space. This is an apparatus for producing a plate-like polymer by moving the composition through a hot water polymerization zone and a heat treatment zone where the composition is polymerized, and continuously taking out a plate-shaped polymer from the other end between the moving bands.

and a mechanism for maintaining contact between the gasket and the self-moving band and setting and maintaining the interval between the bands at a predetermined distance depending on the intended thickness of the plate-shaped heavy metal object, and the polymerizable liquid composition. This device is equipped with a mechanism that follows changes in volume due to polymerization.

Further, as the material of the moving band in the manufacturing apparatus used in the present invention, an endless band made of metal such as copper or stainless steel is preferable, but it is also possible to use a plastic film overlaid on the metal band. When the plastic film used over the metal band has an uneven surface, the surface of the resulting plate-like polymer can be patterned with the uneven surface. Generally, when using metal foil, it is preferable to use one having a thickness of 0.1 to 3 g+, particularly 0.5 to 2=.

The polymerizable liquid composition of the present invention is caused to run together with the moving band and is heated from outside the moving band to polymerize the composition, and the heating zone is divided into a hydrothermal polymerization zone and a heat treatment zone. . In the hot water polymerization zone, the band is heated by spraying hot water in a shower or by running the moving band in a hot water bath.
The hot water temperature may be constant throughout the hydrothermal polymerization zone, or may be varied stepwise or continuously. The polymerizable liquid composition of the present invention is polymerized while traveling through the hydrothermal polymerization zone together with the moving band, and generally reaches a conversion rate of 80 to 96% by weight, with the remainder being polymerized in the heat treatment zone.

Therefore, since most of the bundling reactions take place in the hydrothermal polymerization zone, the polymerization in this zone is particularly commonly referred to as main polymerization.

The polymerizable liquid composition of the present invention travels through a heat treatment zone together with the moving band following the hydrothermal polymerization zone,
In this heat treatment zone, heating is performed by applying hot air to the outside of the moving band or by using a far-infrared heater, and the heat treatment temperature may be constant throughout the heat treatment zone or may be changed stepwise or continuously. The polymerizable liquid composition of the present invention undergoes substantially complete polymerization by the end of this heat treatment section.

In this way, the polymerizable liquid composition of the present invention is supplied to the space between the moving bands, and substantially completes its polymerization while passing through the hydrothermal polymerization zone and the heat treatment zone together with the moving bands, A plate-shaped polymer is taken out from the other end between the moving bands, and a cooling area is provided following the heat treatment area,
It is desirable to cool the polymer plate before taking it out. Generally, it is desirable to cool the plate-shaped polymer so that the temperature of the plate-like polymer when taken out is 100°C or less, preferably 90°C or less, and cooling can be done by spraying cold water or cold air in layers on the outside of the moving band. Alternatively, there are methods such as applying heat or cooling at room temperature. ``Next, an example of the manufacturing apparatus used in the present invention will be specifically explained with reference to the drawings.

In FIG. 5, endless bands 1 and 2 are tensioned by pulleys 8 and 4 and pulleys 6 and 6, respectively, and pulleys 4 and 6 are driven at the same circumferential speed to run bands 1 and 2, and the pulleys at one end 4. Pour the polymerizable liquid mixture through the openings of 8 and 6. *Continuously supply l, and take out the plate-shaped polymer from the openings of pulleys 4 and 6 at the other end.

Figure 5 shows the case where the lower band is longer than the upper band, and the cooling of the hydrothermal polymerization zone and heat treatment zone from the point where main polymerization starts, ie point A, to the end point of the cooling zone, ie point F. It represents the positional relationship of areas. That is, in FIG. 5, the area from point A to point D represents the hydrothermal polymerization zone, the area from point D to point E represents the heat treatment area, and the area from point E to point F represents the cooling area. This indicates that the vehicle will pass through the following areas in sequence. Then, moving bands 1 and 2 run in a straight line and incline from point A to point B, with point A positioned well above point B with respect to the horizontal, and run in a concave curve from point B to point C. However, from point C to point F, point F is higher than point C, and the vehicle travels in a straight line at an incline.

In Fig. 6, 1: The upper and lower bands are supported by a non-rotating support body 7 having a frame and a frame structure placed in the area from point A to point B, and the distance between the upper and lower bands is set and maintained at a predetermined distance. In the area from point B to point F, the upper and lower bands are supported by a group of rollers 8, and can easily follow changes in the volume of the polymerizable liquid composition.

Although one example of the manufacturing apparatus used in the present invention has been specifically explained, the apparatus to which the present invention is applied is not limited to this example, and the present invention can be applied to a manufacturing apparatus conventionally known as a continuous casting method. Needless to say, it can be applied. For example, even if the running pattern of the lower band from the supply port to the space between the moving bands of the polymerizable composition to the outlet of the plate-like polymer is horizontal, or straight and inclined, , or may be even more naturally curved. Furthermore, at the supply port of the polymerizable liquid composition into the space between the moving bands, a device or the like may be provided for holding a constant amount of the composition.

The gasket used in the present invention is generally made of plastic string, such as soft polyvinyl chloride,
Flexible plastics such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer rubber, natural rubber, and other rubbers are used as the material. Generally, soft polyvinyl chloride is used, and preferably contains 80 to 170 parts by weight of a plasticizer such as dioctyl phthalate per 100 parts by weight of polyvinyl chloride. The shape of the gasket may be square, rectangular, or circular in cross section, and generally a hollow pipe shape is preferred.

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. The percentages in the examples are percentages by weight.

The heat distortion temperature in the examples is JIS K6718.
Polymerization foaming is determined by observing the obtained plate-shaped polymer with the naked eye to determine the presence or absence of bubbles, and thermal foaming is carried out by placing the obtained plate-shaped polymer in a circulating hot air oven at 180°C. 8
After heating for 0 minutes, determine the presence or absence of bubbles by visual observation.
did. The reduced viscosity was measured by measuring a 0.1% chloroform solution of the obtained plate-like polymer at 25°C, and the residual viscosity was measured by gas chromatography after dissolving the obtained plate-like polymer in methylene chloride. .

Example 1 Width 500111. Using a mirror-finished stainless steel band with a thickness of 0.6 mm, in the continuous polymerization apparatus shown in Figure 6, the horizontal distance from point A to point B, where hydrothermal polymerization starts, is 2,900 U, and the distance between A and H is a straight line. big and horizontal 8
''The upper and lower bands are supported by non-rotating supports of frame structure, and the horizontal distance between BC is 2.240.
At, it is curved concavely with an oil rate radius of 25.428 a, and the upper and lower bands are supported by rollers, and the CF is a straight line with a horizontal distance of 4.860 ml, which is 2.10 mm from the horizontal.
Tilt, tilt, and support the upper and lower bands with rollers! '1 Of the AF horizontal distance of 10,000a+, there is a hydrothermal polymerization zone where 6,240@l between AD is heated with 80℃ hot water and a heat treatment zone where 2.670111 between DE is heated with 120℃ hot air. An apparatus equipped with a cooling area capable of cooling the 1,09- space between the and EF with cold air was used.

From one end on the A point side of this device, between the upper and lower bands, 0.001% azobisisobutyronitrile was added to methyl methacrylate containing 8% ethyl acrylate and polymerized at 80°C.The viscosity at 25°C was 18 Polymerization rate is 20% with Poise
Cumylperoxyneodecanoate 0.9
2% (B, OX 10-
3 mole parts) was dissolved and degassed under reduced pressure, and the solution was continuously supplied together with a hollow pipe-shaped soft polyvinyl chloride containing 65% of dioctyl phthalate, and 54% of the solution was dissolved in the upper band.
9- Apply an initial tension of 4 kQ/wJ to the lower band, drive the band at a speed of 645 1/min, and adjust the upper and lower band spacing between AB so as to obtain a plate-like polymer with a thickness of 8-. The sillage is polymerized as it passes through a hydrothermal polymerization zone and a heat treatment zone, and is cooled in a cooling zone to form a plate-shaped polymethyl methacrylate sheet with a thickness of about 8 mm that is transparent and shows no polymerization foaming at the other end of the apparatus. Got the product. At this time, the polymerization times in the hot water polymerization zone and the heat treatment zone were 10.0 minutes and 4.8 minutes, respectively, which were extremely short times.

The reduced viscosity of the obtained product is 1.4 del? The reverberation monomer content was 0.5%, the heat distortion temperature was 101°C, and no thermal foaming was observed. Furthermore, no change was observed on the surface of the obtained product when it was exposed to ethyl acetate vapor for 1 hour.

Example 2 0.00-1% azobisisobutyronitrile was added to methyl methacrylate containing 8% ethyl acrylate and polymerized at 80°C.The viscosity at 25°C was 7 voids and the polymerization rate was 15%. cumylperoxyneodecanoe) 2.15% (for 100 parts by weight of Shirabu,
7.0 x 10-3 mole parts) was dissolved and degassed under reduced pressure, and then fed to the apparatus of Example 1 for polymerization. At this time, the temperature in the heat treatment zone was 120° C., but the temperature in the hydrothermal polymerization zone and the band cutting speed were changed from those in Example 1, and the results shown in Table 1 were obtained.

In all of the obtained plate-shaped transparent polymethyl methacrylate products with a thickness of about 8 M, no polymerization foaming was observed despite the short polymerization time, and no thermal foaming was observed.

Example 8 Azobisisobutyronitrile o, o to methyl methacrylate containing an appropriate amount of 2-ethylhexyl acrylate
ot% was added and polymerized at 80°C to obtain a sill with a viscosity of 20 poise at 25°C and a polymerization rate of 25%.

Add to this 0.92% cumyl peroxyneodecanoate (
The apparatus of Example 1, in which the temperature in the hydrothermal polymerization zone is 80 °C and the temperature in the heat treatment zone is 126 °C, after dissolving and degassing under reduced pressure The polymerization was carried out by supplying the polymer at a moving speed of 594 cm and driving at 1 w/min. At this time, the polymerization time in the hot water polymerization zone and the heat treatment zone was 1000 hrs.
It was a very short time, 4.6 minutes.

In the obtained transparent polymethyl methacrylate product in the form of a plate of about 9 am, no polymerization foaming was observed despite the short polymerization time, and no thermal foaming was observed.

Example 4 Methyl methacrylate containing an appropriate amount of butyl acrylate and azobisisobutyronitrile o,oot% were added and polymerized at 80°C to produce a silica with a viscosity of 20 poise at 25°C and a polymerization rate of 25%. I got it. After dissolving 0.92% of cumyl peroxyneodecanoate (8.0 mol parts per 100 parts by weight of silica) and degassing under reduced pressure, the temperature of the hydrothermal polymerization zone I was set to 80°C. Polymerization was carried out by feeding into the apparatus of Example 1 in which the temperature of the heat treatment zone was 126C, and the results shown in Table 2 were obtained.

...'i In all of the obtained plate-shaped transparent polymethyl methacrylate products with a thickness of about 8M, no polymerization foaming was observed despite the short polymerization time, and no thermal foaming was observed.

Example 5 Methyl methacrylate containing 8% ethyl acrylate was charged into a polymerization reactor equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirring device, and the temperature was raised to 90°C while stirring while maintaining a nitrogen atmosphere inside the reactor. After raising the temperature, 0.08% of 2°2'-azobis(2,4-dimethylvaleronitrile) was added. A temperature rise due to polymerization heat was immediately observed, and the temperature rose to 100
After being held under reflux conditions at ~102°C for 10 minutes, the reactor was cooled. The sillage obtained at this time had a viscosity of 20 poise at 25° C. and a polymerization rate of 25%.

After dissolving an appropriate amount of cumyl peroxyneodecanoate in this sill slub and degassing it under reduced pressure, it was fed to the charge of Example 1 in which the temperatures of the hydrothermal polymerization zone and the heat treatment zone were changed, and polymerization was carried out. 8 results were obtained.

In all of the obtained plate-like transparent polymethyl methacrylate products with a thickness of about 8W, no polymerization foaming was observed despite the short polymerization time, and no thermal foaming was observed.

About 8
Example 8 Polymerization of Example 6 In all of the double-opened polymethyl methacrylate products in the form of a plate with a thickness of 100 mm, no polymerization foaming was observed despite the short polymerization time, and no thermal foaming was observed. Methyl methacrylate was charged into a reactor, 0.1% of 2.2'-azobis(2゜4-dimethylvaleronitrile) was added at 90°C, and polymerization was carried out under reflux conditions until the viscosity at 25°C was 40 poise. A silica with a polymerization rate of 80% was obtained. After dissolving a suitable amount of cumyl peroxyneodecanoate in this sill slub and degassing it under reduced pressure, it was fed to the apparatus of Example 1 in which the temperatures of the hydrothermal polymerization zone and the heat treatment zone were changed, and polymerization was carried out as shown in Table 6. The result was 1'1□'. Ma: (5゜) In all of the plate-shaped transparent polymethyl methacrylate products with a thickness of approximately □.8a obtained, no polymerization foaming was observed despite the short polymerization time, and no thermal foaming was observed. Ta.

Example 9 Methyl methacrylate containing 6% of ethyl acrylate was charged into the polymerization reactor of Example 5, and 0.08% of 2,21-azobis(2,4-dimethylvaleronitrile) was added.
The mixture was added at 0°C and polymerized under reflux conditions to obtain a sillage with a viscosity of 20 poise at 25°C and a polymerization rate of 25%.

Kumi k/'? -4th cineodecanoe) 0.92% (8.92% for 100 parts by weight of silica)
After dissolving 0XlO-'molar parts) and degassing under reduced pressure,
The temperature in the hydrothermal polymerization zone is 86℃, and the temperature in the heat treatment zone is 12℃.
The mixture was supplied to the apparatus of Example 1 at 5° C., and polymerization was carried out by performing one movement at various band movement speeds, and the results shown in Table 7 were obtained.

In all of the obtained plate-shaped transparent polymethyl methacrylate products with a thickness of about 8W, no bonding foaming was observed, nor was any heat foaming observed. Furthermore, from Table 7, it is clear that even if the polymerization time is shortened, there is no problem in terms of quality.

Example 1G Methacrylic resin (trade name SUMIPEX-B MW, manufactured by Sumitomo Chemical Industries, Ltd.) 2596 was dissolved in methyl methacrylate, ethyl acrylate 896 was added thereto to make a silage, and an appropriate amount of cumyl peroxyneodecanoate was added. It was dissolved, degassed under reduced pressure, and fed to the apparatus of Example 1 in which the upper and lower band spacing between A and B was adjusted to obtain a plate-like polymer with a thickness of 4 mm, and a hydrothermal polymerization zone and a heat treatment zone 1. Then, polymerization was carried out by driving at various band movement speeds, and the results shown in Table 8 were obtained.

In all of the obtained plate-shaped transparent polymethyl methacrylate products with a thickness of about 4 mm, the polymerization time was short and no polymerization foaming was observed despite the increased thickness, and no foaming was observed due to heating. There wasn't.

Example 11 An appropriate amount of cumyl peroxyneodecanoate was dissolved in the silica obtained in Example 9 and degassed under reduced pressure to obtain a plate-like polymer having a thickness of 5 mg with an upper and lower band interval between AB. The apparatus of Example 1, which had been adjusted as described above, was supplied and polymerization was carried out by varying the temperature of the hydrothermal polymerization zone and the speed of the band spectrometer to obtain the word list shown in Table 9.

In all of the obtained plate-shaped transparent polymethyl methacrylate products with a thickness of about 5 m, no polymerization foaming was observed despite the increased thickness, and no thermal foaming was observed.

15. ...). Example 12 Methyl methacrylate was charged into the polymerization reactor of Example 5, 0.08% of 2.21-azobis(2゜4-dimethylvaleronitrile) was added at 90°C, and polymerization was carried out under reflux conditions. The viscosity at 25°C is 20 poise and the polymerization rate is 25%.
I got the syllabus.

Add 0.75% of a 70% dibutyl phthalate solution of isopropyl cumyl peroxyneodecanoate (
The same neodecanoate is added to 100mm of Shiratubu.
．． After dissolving 5xto-a molar parts) and degassing under reduced pressure,
The temperature in the hydrothermal polymerization zone is 80℃, and the temperature in the heat treatment zone is 12℃.
When fed to the apparatus of Example 1 at 0°C, the band movement speed was 62
Polymerization was carried out by driving at 4 M/min. At this time, the polymerization time in the hot water polymerization zone and the heat treatment zone was 10.
They were 0 minutes and 4.8 minutes.

The resulting transparent plate-shaped polymethyl methacrylate product with a thickness of approximately 8all and no visible polymerization foaming had a reduced viscosity of 2.1 dll/f, a residual monomer content of 0.7%, and a heat distortion temperature of 108°C. No thermal foaming was observed.

Further, even when the obtained product was exposed to ethyl acetate vapor for 1 hour, no change was observed in its surface appearance.

Example 18 The silica obtained in Example 12 was mixed with 70% dibutyl phthalate of isopropyl cumyl peroxyneodecanoate. 1 mol part) was dissolved and degassed under reduced pressure. Then, the apparatus of Example 1, in which the spacing between the upper and lower bands was adjusted so that the thickness of the plate-shaped polymer obtained was 4 m, was supplied, and hot water was added to the mixing area. The temperature of
Polymerization was carried out by driving at 6+/min.

The length of the obtained plate-shaped polymethyl methacrylate product was approximately 4 m, and no polymerization foaming was observed. Also, the reduced viscosity of the product is 2.1 dll? .

The residual monomer content was 0.6%, the heat distortion temperature was 104°C, and no thermal foaming was observed.

Example 14 A 70% dibutyl phthalate solution of isopropyl cumyl peroxy neodecanoate (0.85%) was added to the silica obtained in Example 12 (0.7 x 1 G-3 mol of the same neodecanoate per 100 parts by weight of silica). part) was dissolved and degassed under reduced pressure. Example 1 in which the upper and lower band intervals were adjusted so that the thickness of the plate-like polymer obtained was 6-
The temperature of the hydrothermal polymerization zone was set to 76°C, the temperature of the heat treatment zone was set to 120°C, and the band movement speed was set to 41°C.
Polymerization was carried out by driving at 6111/min.

The resulting transparent plate-like polymethyl methacrylate with no polymeric foaming and approximately 5 mm thick had a reduced viscosity of 1.
76g/l, residual monomer 0.5%, heat distortion temperature 1
The temperature was 08°C, and no thermal foaming was observed.

Example 15 A 50% toluene solution of 2-ethylhexylmilperoxyneodecanoate was added to the silica obtained in Example 8.
, 59% (0.7 x 10-'' mole part of the same neodecanoate per 100 parts by weight of silica) was dissolved and degassed under reduced pressure, and the temperature in the hydrothermal polymerization zone was 80°C and the temperature in the heat treatment zone was 180°C. was supplied to the apparatus of Example 1, and the polymerization was carried out by driving at a band movement speed of 520-7 minutes.At this time, the polymerization times in the hydrothermal polymerization zone and the heat treatment zone were 12.0 minutes and 5.18 minutes, respectively. It was a minute.

The resulting transparent plate-shaped polymethyl methacrylate 111 product with a thickness of approximately 8M with no visible polymerization foaming had a residual monomer content of 0.7% and a heat distortion temperature of 1.
The temperature was 08°C, and no thermal foaming was observed. Further, when the obtained product was exposed to ethyl acetate vapor for 1 hour, no change was observed on its surface.

Example 16 60% toluene #! of ethoxyethyl cumyl peroxy neodicanoate was added to the silicula obtained in Example 7. 7fi
After dissolving 2.27% (8.OX 1 G-' mole parts of neodecanoate per 100 parts by weight of silica) and degassing under reduced pressure, the temperature in the hot water polymerization zone 11 was 800, the temperature in the heat treatment zone, was supplied to the apparatus of Example 1 at a temperature of 180° C., and polymerization was carried out by driving at a band movement speed of 784,114. At this time, the polymerization times in the hydrothermal polymerization zone and the heat treatment zone were 8.6 minutes and 8.6 minutes, respectively.

The resulting transparent plate-shaped polymethyl methacrylate product with a thickness of about 8 W and no visible foaming had a reduced viscosity of 1.
．． 8 di/f, residual monomer content was 0.6%, heat distortion temperature was 97°C, and no foaming was observed. Further, when the obtained product was exposed to ethyl acetate vapor for 1 hour, no change was observed on its surface.

Reference Example 1 Example 1 in which the lauroyl peroxide in the device was dissolved in the sill sludge obtained in Example 9 and degassed under reduced pressure, and the temperature in the hydrothermal polymerization zone was 80C1 and the temperature in the heat treatment zone was 120C. The polymer was supplied to a device shown in Table 1, and polymerization was carried out by driving the band at different speeds to obtain a plate-shaped polymer having a thickness of about 8M as shown in Table 1o.

Table 10 shows that when lauroyl peroxide is used as a polymerization initiator and polymerization is carried out for a certain amount of time, the shorter the polymerization time, the more polymerization foaming occurs, and furthermore, thermal foaming occurs in both cases, which is not preferable.

d equivalent of 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in the sillage obtained in Example 5 and degassed under reduced pressure. Example 1 The temperature was 120° C., and polymerization was carried out by changing the band movement speed.
A plate-shaped polymer having a thickness of about 8 mm was obtained.

From Table 11, 2,2'-azobis(2
, 4-dimethylvaleronitrile) in a short time, the shorter the polymerization time, the more polymerization foaming occurs, and heat foaming occurs in both cases, which is undesirable.
.

No reference example 8 Methacrylic resin (trade name Sumipex-B MW, Sumitomo Chemical mws, > 2 to methyl methacrylate)
After dissolving 5% of methyl acrylate and adding 8% of methyl acrylate to make a sillage, dissolving cumyl peroxyneodecanoate and degassing under reduced pressure, the temperature of the hydrothermal polymerization zone and the heat treatment zone was changed. Polymerization was carried out using the same equipment as in Example 1 to obtain a plate-shaped polymer having a thickness of about 9 am as shown in Table 12.

Table 12 shows that when the amount of wax as a polymerization initiator is larger than the range of the present invention, the polymerization time becomes very short and polymerization foaming does not occur, but heating foaming occurs, which is not preferable.

On the other hand, even if the amount of polymerization initiator is appropriate, if the temperature of the hydrothermal polymerization zone exceeds the range of the present invention, polymerization foaming will occur and the polymerization will not be completed, resulting in the residual upper layer becoming extremely large. This is not desirable because it increases the number of people.

Reference Example 4 Methacrylic 1111M (trade name Sumipex-B MW, manufactured by Sumitomo Chemical Industries, Ltd.) was added to methyl methacrylate for 25 minutes.
After dissolving cumyl peroxyneodecanoate and degassing it under reduced pressure, it was fed to the apparatus of Example 1 in which the temperature of the hydrothermal polymerization zone was changed to prevent polymerization and foaming. Polymerization was carried out while adjusting the band cutting speed, and the results shown in Table 18 were obtained.

No polymerization foaming or heat foaming was observed in any of the obtained plate-shaped polymethyl methacrylate products with a thickness of about 8M. However, from Table 18, when the amount of polymerization initiator is less than the range of the present invention, ``, 1 or when the temperature of the hydrothermal polymerization zone is lower than the range of the present invention even if the polymerization initiator is properly filtered. Both are unfavorable because the polymerization time becomes longer and productivity decreases.

Reference example 5 0 azobisisobutyronitrile in methyl methacrylate
．． A 70% solution of isopropyl cumyl peroxyneodecanoate in dibutyl phthalate (0.85%) was added to a silica with a viscosity of 2 Boise at 25°C and a polymerization rate of 8.4%. (0.70 x 1G 4 mol parts of neodecanoate per 100 parts of Shirabu) was dissolved and degassed under reduced pressure, and the temperature in the hydrothermal polymerization zone was 85.
The polymerization was carried out by supplying the polymer to the apparatus of Example 1 with a heat treatment zone temperature of 180° C. and driving at a band transfer linkage of 812a+4/min.

At this time, although the polymerization time in the hot water polymerization zone and the heat treatment zone took a long time, 20 minutes and 8.6 minutes, respectively, the polymerization in the hot water polymerization zone had not progressed sufficiently, so foaming occurred in the heat treatment zone. However, it was not possible to obtain a plate-shaped polymer with a satisfactory thickness of about 8 m.

Reference Example 6 A 70% dibutyl phthalate solution of isopropyl cumyl peroxyneodecanoate was added to the silica of Example 126.
0% (1.OX 1 G-2 mole parts of neodecanoate per 100 parts by weight of silica) was degassed under reduced pressure, and the temperature in the hydrothermal polymerization zone was set to 55°C and the temperature in the heat treatment area to 180°C. Supplied to the apparatus of Example 1, band movement speed 2
Polymerization was carried out by driving at 401/min.

At this time, although the polymerization time in the hot water polymerization zone and the heat treatment zone took a long time, 26 minutes and ti minutes, respectively, the polymerization did not proceed sufficiently in the hot water polymerization zone, so foaming occurred in the heat treatment zone. However, it was not possible to obtain a plate-shaped polymer with a satisfactory thickness of about 8 mm.

:・.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between the molar parts of cumyl peroxyneodecanoate and/or monoalkyl cumyl peroxyneodecanoate and the temperature of the hydrothermal polymerization zone, based on 100 parts by weight of sillage within the range of the present invention. , second
Figures 4 to 4 show the relationship between the molar parts of cumyl peroxyneodecanoate or/and monoalkyl cumyl peroxyneodecanoate per 100 parts by weight of syllabary and the temperature of the hydrothermal polymerization zone under certain conditions. This is a graph showing. The fifth leap is a longitudinal section Ifi diagram of a continuous polymerization apparatus as an example for carrying out the present invention. In the figure, 112 is a moving band;
8.4.5.6 is a pulley, 7 is a support, 8 is a roller, A, D is a hydrothermal polymerization zone, D, E is a heat treatment zone, K, F
indicate cooling zones, respectively. 1

Claims (1)

[Scope of Claims] (1) Two consecutive moving bands in an upper and lower relationship are made to run in the same direction at the same speed, and at least one continuous gasket is provided on both sides of each moving band as a self-moving band. The spaces between the moving bands are sealed by running in contact with each other, and cumyl peroxyneodecanoate or/and monoalkyl is added as a polymerization initiator to the silica with a polymerization rate of 15 to 35%, which is mainly composed of methyl methacrylate. A polymerizable liquid composition in which cumyl peroxyneodecanoate is dissolved is continuously supplied into the space between the moving bands, and the composition is caused to run through the hydrothermal polymerization zone where the composition polymerizes together with the self-moving band. In this case, the relationship between the number of molar parts and the temperature (C) of the hydrothermal polymerization zone based on 100 parts by weight of cumyl peroxy neodecanoate or/and monoalkyl cumyl peroxy neodecanoate gun 921 as a polymerization initiator. is point A (IXI
O-', 90), B (IXIO'. 85), C (8X10-160), 1) (IXIO86
Polymerization is carried out under the conditions of a closed region formed by connecting each point to 5 with a straight line, and the polymerization is completed by passing through the last heat treatment area, and the plate-shaped polymer is removed from the other end between the moving bands. Continuous polymerization method characterized by taking out. (2) Monoalkyl cumyl peroxy neodecanoate, which is a polymerization initiator, is isopropyl cumyl peroxyne, odecanoate, n-butyl cumyl peroxy neodecanoate 3, inbutyl cumyl peroxy neodecanoate, 5ec-butyl cumyl peroxyne, and 5ec-butyl cumyl peroxyneodecanoate. Toxicumyl peroxyneodecanoate, tertiary butyl cumyl oxyneodecanoate, 2-ethylhexyl methyl peroxyneodecanoate, toxicumyl peroxyneodecanoate, 8 - ethoxybutylcumyl peroxyneodecanoate. (8) The continuous polymerization method according to claim 1, wherein the silica granules have a viscosity of 6 voids or more at 26°C. The continuous polymerization method according to claim 1, wherein the continuous polymerization method comprises: (5) The acrylic acid alkyl ester (however, the alkyl group has 1 to 8 mature wood atoms) to be contained in the shirabu is methyl acrylate, ethyl acrylate, normal butyl acrylate, isopropyl acrylate,
At least one selected from normal butyl acrylate, imbutyl acrylate, '5ec-butyl acrylate, tert-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, and octyl acrylate, based on the total weight of 5. The continuous polymerization method according to claim 4, wherein the content is 0.5 to 15j1% by weight. (6) The continuous polymerization method according to claim 1, wherein the temperature of the heat treatment zone is 110 to 150°C.