JPH0224850B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a terephthalic acid diallyl ester copolymer which has not been described in any prior art literature, and which can substantially maintain the desirable properties of the terephthalic acid diallyl ester polymer and has improved bending strength and significantly improved impact resistance. The present invention relates to a terephthalic acid diallyl ester copolymer exhibiting properties. In particular, terephthalic acid diallyl ester and at least one at the benzylic position
This is a terephthalic acid diallyl ester copolymer that is composed of an aromatic hydrocarbon having hydrogen atoms and has not been described in any known literature. The present invention relates to a terephthalic acid diallyl ester copolymer that exhibits excellent properties, particularly excellent impact resistance, and can be easily molded, and is useful as, for example, engineering plastics. The invention also relates to a method for making such copolymers. More specifically, the present invention is based on the following formula () Terephthalic acid diallyl ester represented by and the following formula (2) However, in the formula, R ¹ and R ² each represent a group selected from the group consisting of a hydrogen atom and a lower alkyl group, n represents an integer of 1 to 3, and at least one benzyl position represented by Derived from an aromatic hydrocarbon having a hydrogen atom, the following formula (3) and the following formula (4) A terephthalic acid diallyl ester copolymer having a repeating unit of (a) one monomer unit of the formula (2) at the end of the monomer unit of the formula (1), and one monomer unit of the formula (1) at the benzyl position; ) has a carbon-carbon bond structure with the allyl group of the monomer unit and its ₃ C and/or ₃ ′ C, and (b) the carbon formed by the allyl group of the monomer unit of formula (1) in the copolymer. - the formula of the carbon-bonded molecular chain moiety;
(1) The number of monomer units is 3 to 11, preferably 3
(c) the degree of unsaturation expressed as an iodine number measured by the Wijs method is from 40 to 85, preferably from 45 to 80;
(d) true specific gravity at 25°C is 1.20 to 1.25, preferably 1.21 to 1.25, and (e) number average molecular weight (n) in terms of polystyrene measured by GPC (gel permeation chromatography) method. 4,000 to 10,000, a weight average molecular weight (w) of 70,000 to 200,000, and (f) a molecular weight distribution expressed as the ratio w/n of n and w of 10 to 40. This invention relates to a diallyl ester copolymer. Conventionally, diallyl phthalate resin has excellent mechanical properties such as dimensional stability and rigidity under heat, heat resistance, and electrical properties, and has been widely used in fields that require high reliability. Resins are brittle and have insufficient toughness, and in recent years, with the miniaturization of molded products, the problem of cracking and chipping in thin parts and small protrusions of the molded products has become more serious. In order to overcome these technical problems, many proposals have been made to improve the brittleness of diallyl phthalate resins by improving blending techniques and polymer blends. For example, methods of reinforcing with fillers such as glass fibers, and methods of modifying with flexible polyester or rubber-like polymers are known. However, although all of these methods were intended to impart toughness to diallyl phthalate without impairing its excellent properties, it cannot be said that they have achieved their objective. For example, in the method using the filler described above,
It is necessary to leave the long fiber filler in the molded product, but this imposes significant restrictions on the kneading method and molding method, making it impractical. In addition, in the method of modifying with other polymers etc. mentioned above, dimensional stability,
Usually, any one of heat resistance, mechanical strength, electrical properties, and moldability is unduly reduced. As described above, the conventionally proposed methods have reached their limits of improvement, and the current situation is that the conventionally proposed methods cannot offer much in order to achieve satisfactory improvements. On the other hand, polybutylene terephthalate (PBT)
Thermoplastic resins such as PPS and polyphenylene sulfide (PPS) have made remarkable progress, and resins and compounding techniques with excellent heat resistance and electrical properties have been developed, and they are also highly productive. It has come to be adopted in a wide range of fields, including fields where thermosetting resins are used. However, since it is a thermoplastic, there are problems with deformation due to creep and heat resistance, and its reliability is not as high as that of thermosetting resins, especially when used for long periods of time under high temperature and high humidity conditions. The present inventors have discovered that the resin has properties comparable to or superior to conventional diallyl phthalate resins,
In addition, research has been conducted to develop tough thermosetting resins with improved high impact values. As a result, the terephthalic acid diallyl ester of the formula (1) and the aromatic hydrocarbon having at least one hydrogen atom at the benzyl position represented by the formula (2) form a copolymer. The copolymer is a terephthalic acid diallyl ester copolymer which has not been previously described in the known literature, and which substantially maintains the desirable properties of the terephthalic acid diallyl ester polymer, and furthermore has improved flexural strength and significantly improved flexural strength. discovered that this is a new polymer compound that exhibits high impact resistance. Such knowledge was previously completely unknown. Based on the completely new knowledge that the compound of formula (1) and the compound of formula (2) form a new polymer compound having the above-mentioned excellent properties, further research has revealed that
Terephthalic acid diallyl ester of the above formula (1) and an aromatic hydrocarbon having at least one hydrogen atom at the benzyl position represented by the above formula (2) are combined in a specific controlled manner in the presence of an organic peroxide. By selecting reaction conditions and carrying out the reaction, a copolymerization reaction is carried out with good reaction reproducibility. The allyl group of the monomer unit of formula (1) and its ₃ C and/or
or has a structure in which ₃ ′ C and a carbon-carbon bond are formed, (b),
The number of the formula (1) monomer units in the carbon-carbon bond molecular chain portion formed by the allyl group of the formula (1) monomer unit in the copolymer is 3 to 11, preferably 3 to 10. It has been discovered that novel terephthalic acid diallyl ester copolymers of the present invention having structural characteristics are obtained. Such selection of reaction conditions could only be made with knowledge of the above new findings, and such selection itself was previously completely unknown. Furthermore, the obtained terephthalic acid diallyl ester copolymer, which has not been previously described in any known literature, can be extracted as a so-called prepolymer that can be further cured to become an insoluble and infusible three-dimensional polymer under selected conditions. It was discovered that it is a new thermosetting resin. It has been known that lower aliphatic alcohols and aromatic hydrocarbons can be used as solvents in the polymerization of diallyl terephthalate (for example, Japanese Patent Publication No. 35-943). In addition, a proposal was made to use aromatic hydrocarbons such as cumene and diisopropylbenzene as chain transfer agents as additives in order to improve the polymerization rate in the production of prepolymers of diallyl phthalate (Japanese Patent Publication No. 1973- No. 1832)
is also known. However, as mentioned above, the existence and possible formation of new copolymers having the above-mentioned improved properties were completely unknown, and therefore, any knowledge useful for the formation of such copolymers would not be available in the prior art. has not been developed. Naturally, the copolymerization reaction and copolymer of formula (1) diallyl terephthalate and formula (2) aromatic hydrocarbon have not been described in any known literature, including the above-mentioned prior art. Not yet. As a result of the research conducted by the present inventors, by selecting specific and controlled reaction conditions, the above formula (2 ) The aromatic hydrocarbon having at least one hydrogen atom at the benzylic position specified in formula (1) enters the polymer chain as a copolymerization component of terephthalic acid diallyl ester, and
forming a copolymer having the structural characteristics of (a) and (b);
It has been discovered that this copolymer is an extremely useful new copolymer exhibiting the excellent improved properties mentioned above. Therefore, an object of the present invention is to provide a novel terephthalic acid diallyl ester copolymer and a method for producing the same. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The terephthalic acid diallyl ester copolymer of the present invention has the following formula (1): Terephthalic acid diallyl ester represented by and the following formula (2) However, in the formula, R ¹ and R ² each represent a group selected from the group consisting of a hydrogen atom and a lower alkyl group, n represents an integer of 1 to 3, and at least one benzyl position represented by Derived from an aromatic hydrocarbon having a hydrogen atom, the following formula (3) and the following formula (4) A terephthalic acid diallyl ester copolymer having a repeating unit of (a) one monomer unit of the formula (2) at the end of the monomer unit of the formula (1), and one monomer unit of the formula (1) at the benzyl position; ) has a carbon-carbon bond structure with the allyl group of the monomer unit and its ₃ C and/or ₃ ′ C, and (b) the carbon formed by the allyl group of the monomer unit of formula (1) in the copolymer. - the formula of the carbon-bonded molecular chain moiety;
(1) The number of monomer units is 3 to 11, preferably 3
(c) the degree of unsaturation expressed as an iodine number measured by the Wijs method is from 40 to 85, preferably from 45 to 80;
(d) true specific gravity at 25°C is 1.20 to 1.25, preferably 1.21 to 1.25, and (e) number average molecular weight (n) in terms of polystyrene measured by GPC (gel permeation chromatography) method. 4,000 to 10,000, a weight average molecular weight (w) of 70,000 to 200,000, and (f) a molecular weight distribution expressed as the ratio w/n of n and w of 10 to 40. It is an acid diaryester copolymer. According to one preferred embodiment of the present invention, the copolymer of the present invention further has any of the following properties. (g) Softening range 50 to 120°C, preferably about 60° to about
110°C, more preferably about 70° to about 100°C, (h) viscosity of 50% by weight methyl ethyl ketone solution 80 to
300 centipoise (30 DEG C.); (i) a Brabender melt viscosity of 250 to 2600 m.g, preferably 400 to 2500 m.g, as measured by a Brabender plastograph; and a processing time of 5 to 65 minutes. As mentioned above, the terephthalic acid diallyl ester copolymer of the present invention has one monomer unit of the formula (2) at the terminal of the monomer unit of the formula (1) (a), and the monomer unit of the formula (1) at the benzyl position. It has a structure in which the allyl group of the monomer unit and its ₃ C and/or ₃ ' C are carbon-carbon bonded. Furthermore, (b) the number of formula (1) monomer units in the carbon-carbon bond molecular chain portion formed by the allyl group of the formula (1) monomer unit of the copolymer is 3 to 11, preferably 3 to 11; It has a structural feature of 10 pieces. This structure is converted into toluene (R ¹
=R ² =H, n=1) is used as an example.
It can be shown as below. In the structural part of formula (A) above, R is an unreacted allyl group CH ₂ =CH-CH ₂ - and/or a chain derived from an allyl group constituting another molecular chain part of the copolymer. represents. As an example of such an embodiment, the following formula (C ₁ ) The structural part (C ₁ ) represented by can be mentioned. In the above formula (A) structural part, the number of formula (1) monomer units in the carbon-carbon bond molecular chain part formed by the allyl group of the formula (1) monomer unit is 3 to 3 as shown in formula (A).
11, preferably 3-10. This carbon-carbon bond molecular chain part [formula (B) structural part] is the following head-to-tail bond [formula (B ₁ ) structural part] shown in the above formula (A). In addition to this, it can have the following head-to-head bonding moiety [formula (B ₂ ) structural moiety]. The formula (1) monomer unit in the above structural part (C ₁ ) constitutes a branch point that connects two formula (B) structural parts via two ester bonds. Further, when R is an unreacted allyl group, it can be represented by the following formula (C ₂ ). This formula (C ₂ ) structural part is a part that becomes a crosslinking point during curing of the terephthalic acid diallyl ester copolymer of the present invention. The double bond of the allyl group in this (C ₂ ) structural part accounts for the major part (approximately 90% or more) of the degree of unsaturation expressed by the iodine value measured by the (c) Wijs method described later. As explained above, the terephthalic acid diallyl ester copolymer of the present invention has (a) one monomer unit of formula (2) at the end of the monomer unit of formula (1), at the benzyl position of the monomer of formula (2). (b) has a structure in which the allyl group of the monomer of formula (1) and its ₃ C and/or ₃ ' C are bonded to carbon-carbon, and (b) the allyl group of the monomer unit of formula (1) of the copolymer The carbon-carbon bond molecular chain moiety [formula (B) structural moiety] formed by the formula (1) has a structural feature of 3 to 11 monomer units, preferably 3 to 10 monomer units. The above structural features (a) and (b) of the terephthalic acid diallyl ester copolymer of the present invention are characterized by the excellent dimensional stability, thermal rigidity, heat resistance, electrical properties, etc. of the terephthalic acid diallyl ester copolymer. Improved properties such as improved bending strength, significantly improved impact resistance, and ease of molding while maintaining the same properties.
It is largely involved in combination with other features (b) to (f). The above structural characteristics (a) and (b) of the copolymer of the present invention are measured and determined in the following manner. Method for measuring and confirming structural characteristics (a) and (b): - Place the sample terephthalic acid diallyl ester copolymer in a vacuum dryer, reduce the pressure with an oil rotary vacuum pump and a diffusion pump at room temperature, and dry until it reaches a constant weight. . The above dried copolymer was dissolved in chloroform-d to a concentration of 10 to 20% by weight, and
Measure proton NMR at °C. 60~300MHz
NMR equipment can be used. From the same spectrum, it was confirmed that the copolymer had a structure consisting of monomer units of formula (1) and monomer units of formula (2), and at the same time, the ratio of the number of hydrogen atoms in each aromatic nucleus was determined. Find the ratio of monomer units of formula (1) and monomer units of formula (2) in. 100 parts by weight of the above dried copolymer was heated under reflux for 24 hours with ethanolic 1N potassium hydroxide (135 parts by weight of special reagent grade potassium hydroxide dissolved in 2400 parts by volume of 99.5% ethanol). Hydrolyze and cleave the ester bond. The reaction product is filtered, the filtrate is acidified with hydrochloric acid, filtered again, and the filtrate is concentrated under reduced pressure.
While filtering out the precipitate generated during concentration, remove volatiles in a water bath at 50-70°C and below 5 mmHg until the weight reaches a constant weight. The obtained evaporation residue is used as a hydrolyzate. The above hydrolyzate was dimethyl sulfoxide- _d6
The solution is dissolved in water to a concentration of 5 _{to 10% by weight, and the proton and 13C} ^- NMR spectra are measured. Proton NMR 60~90MHz, room temperature~100℃
to confirm the structure in which monomer units of formula (2) are chemically bonded to polyallyl alcohol. Also,
From the ratio of the number of hydrogen atoms at the benzyl position of the side chain alkyl group of the monomer unit of formula (2) to the number of hydrogen atoms at other positions, it is confirmed that only one hydrogen at the benzyl position has reacted. ¹³ C-NMR is measured at 90MHz and 40°C and integrated 50,000 to 60,000 times to obtain a spectrum. From the same spectrum, when n≠1 in the formula (2) monomer, there are two types of carbon atoms: the benzyl carbon atom bonded to polyallyl alcohol through a carbon-carbon bond, and the benzyl carbon atom remaining unreacted. By confirming this and comparing it with the structure determined from proton NMR, the structure of a hydrolyzate in which the monomer of formula (2) is bonded to polyallyl alcohol at one end at its benzyl position is confirmed. When n=1 in the formula (2) monomer, there is no unreacted carbon atom at the benzyl position, and in the method of the present invention, the carbon atom of the aromatic nucleus does not participate in the copolymerization reaction of the present invention. is not involved (n=0
In other words, in the case of benzene, there is no copolymerization reaction with the monomer of formula (1)), and in this case also, the monomer of formula (2) is bonded to one end of polyallyl alcohol. Measure the mass spectrum of the hydrolyzate.
m/e is {molecular weight of formula (2) monomer - 1} + 58n
Confirm that a peak is shown at the position of (n=0, 2, 3, . . .). As a result of the above, one monomer unit of formula (2) is bonded to the end of the molecular chain portion for each carbon-carbon bonded molecular chain portion formed by the allyl group of the monomer unit of formula (1) in the copolymer. The structure is determined. The molecular weight of the hydrolyzate is determined by vapor pressure osmosis. Model used: Hitachi Perkin Elmer type 115 or 114
Molecular weight measuring device Solvent: Methanol Temperature: 40°C Make 4 to 5 dilute solutions of 1×10 ^-1 to 5×10 ^-1 wt%, use the measuring device to find △R, and use a calibration curve (created using benzyl) Find the apparent molecular weight. Taking the concentration C on the horizontal axis and the apparent molecular weight on the vertical axis, plot each point and extrapolate from C to 0 to obtain the number average molecular weight n.
seek. Subtract {molecular weight of formula (2) monomer - 1} from the calculated molecular weight, and get the molecular weight of allyl alcohol: 58
The number of monomer units of the formula (1) in the carbon-carbon bond molecular chain portion formed by the allyl group of the monomer unit of the formula (1) in the copolymer is determined by dividing by . The terephthalic acid diallyl ester copolymer of the present invention is characterized in that (c) the degree of unsaturation expressed as an iodine value measured by the Wijs method is 40 to 85, preferably 45 to 80. As mentioned above, this iodine value is mainly derived from the double bond of the allyl group in the (C ₂ ) structural part of the copolymer of the present invention. Usually, about 90% or more of the unsaturation is derived from this double bond, and the remainder is the portion of the structure (B) in the structure of formula (A) opposite to the monomer unit of formula (2) ( (described later) may be derived from double bonds that may exist. This (C ₂ ) structural part is a part that becomes a crosslinking point during curing of the terephthalic acid diallyl ester copolymer of the present invention, and when expressed in terms of the number of (C ₂ ) structural parts in one molecule of the copolymer, It is about 6 to about 137. Therefore,
(B) Among the monomer units of formula (1) constituting the structural part, R
is the group CH ₂ =CH−CH ₂ −, i.e., (C ₂ )
The proportion of structural parts is about 43% to about 83%. And the remainder is R

It is recognized that it takes the form of the (C ₁ ) structural moiety represented by the formula and serves as a crosslinking point or branching point between unit chains. The degree of unsaturation expressed in the iodine value of feature (c) above is 40
-85 Preferably 45-80 means that it is relatively low compared to about 80-95 for practical terephthalic acid diallyl ester polymers obtained by conventional methods. , are closely related to the above structural characteristics (a) and (b) in achieving the improved flexural strength and significantly improved impact resistance exhibited by the copolymer of terephthalic acid diallyl ester of the present invention. ,
Furthermore, these and the other features (d), (e) and (f) are subject to the requirements of combination and serve to influence each other. As mentioned above, in relation to structural features (a) and (b), if the iodine value of feature (c) is too small, less than 40,
This causes disadvantages such as unreasonable delay in curing speed, decrease in mechanical strength, decrease in impact resistance, and deterioration in heat resistance.
If the iodine value is too large, exceeding 85, disadvantages such as a decrease in impact resistance, generation of gelled substances during compound formation and other deterioration in processability, and generation of distortion during curing will occur. In the present invention, the iodine value of feature (c) is a value determined by the Wiss method, and is determined by the following method. (c) Method for determining iodine value: - Accurately weigh the sample copolymer within the range of 0.25 to 0.35 g, place it in a 200 ml Erlenmeyer flask with a stopper, and weigh about 30 g.
Add ml of chloroform to completely dissolve the sample. To this, add exactly 20 ml of Wijs reagent (dissolve 7.9 g of iodine trichloride and 8.2 g of iodine in 200 to 300 ml of glacial acetic acid each, then mix both solutions to make 1) using a whole pipette, and then add 2.5 g of iodine to this solution. After adding 10 ml of mercuric acetate glacial acetic acid solution, leave in the dark for 20 minutes to complete the reaction. Add 5 ml of freshly prepared 20% KI solution to this,
Using 1% starch solution as indicator, 0.1N−
Titrate with Na ₂ S ₂ O ₃ standard solution. Shake vigorously during titration. At the same time, also perform a blank reagent. Iodine value = (A-B) × × 1.27/s A: Number of ml of 0.1N-Na ₂ S ₂ O ₃ solution required for blank test B: 0.1N-Na ₂ S ₂ O ₃ solution required for main test Number of ml of 0.1N-Na ₂ S ₂ O ₃ liquid titer s: Number of grams of sample The terephthalic acid diallyl ester copolymer of the present invention preferably has (d) a true specific gravity of 1.20 to 1.25 at 25°C. has the characteristics of 1.21 to 1.25. This true specific gravity means that the true specific gravity of the copolymer of the present invention is relatively low compared to the true specific gravity of conventional terephthalic acid diallyl ester polymers, which is about 1.24 to 1.27. are related to the structural features (a) and (b) above, and furthermore, under the requirements of their combination with other features (c), (e) and (f), they influence each other. It helps improve impact resistance and reduce weight, and also helps maintain good mechanical strength and heat resistance. This characteristic (d) If the true specific gravity is less than 1.20 and is too small,
This causes a decrease in impact resistance, mechanical strength, and heat resistance, and when it is too large, exceeding 1.25, the impact resistance also deteriorates. Incidentally, the true specific gravity of the above feature (d) of the terephthalic acid diallyl ester copolymer of the present invention is a value measured and determined by the following measuring method. (d) Method for determining true specific gravity: - Using a mold, about 7 g of the copolymer is used to make a disc-shaped tablet with a diameter of 30 mm and a thickness of about 10 mm. After repeating the operation of pressurizing at about 570 Kg/cm ² and then releasing the pressure 4 to 5 times to remove air, press at about 1400 Kg/cm ² to form a tablet, sandwich it between 50μ thick polyethylene terephthalate films, and heat it in a high-frequency preheater. After preheating the copolymer to near the softening range, it is pressed at a pressure of about 1400 kg/cm ² for about 30 seconds to form a plate.
The pressing temperature is 10% higher than the upper limit of the softening range of the copolymer.
Set to ~20℃ higher. After removing it from the press and leaving it to cool, visually select a part without air bubbles and break it into a 20 mm square piece to use as a test piece. Measurements are performed in a thermostatic chamber at 25°±0.5°C. The test piece and the ion-exchanged water used for measurement are kept in a constant temperature room overnight to control the temperature. Prepare a jig such as a clip to hang the test piece from the balance. Measure the weight ag of the test piece. Next, the weight cg of the previously prepared jig in water and the total weight bg of the test piece and jig in water by attaching the test piece to the jig are measured. Determine the specific gravity of the test piece using the following formula. Specific gravity of test piece = a/(a-b+c) The average value of the three test pieces is taken as the true specific gravity of the copolymer at 25°C. The terephthalic acid diallyl ester copolymer of the present invention has a number average molecular weight (n) of 4,000 to 10,000 in terms of polystyrene measured by (e) GPC (gel permeation chromatography) method, and a weight average molecular weight (w ) is between 70000 and 200000. This molecular weight is relatively n in the copolymer of the present invention, compared to about 6,000 to 20,000 in conventional terephthalic acid diallyl ester polymers.
Furthermore, compared to the w of conventional terephthalic acid diallyl ester polymers, which is about 60,000 to about 130,000, the copolymer of the present invention has a relatively low w.
This means that the above structural feature (a) is high.
and (b), and in addition, these and other features (c), (d)
and (f), affecting each other,
Improving impact resistance and mechanical strength, maintaining heat resistance,
It is also useful for improving processability and moldability. If the above n and w are too small, the viscosity of the copolymer will decrease, the softening range will decrease, the hardness of the cured product will decrease,
This may cause inconveniences such as deterioration of mechanical strength, and
If it is too large, it will cause a decrease in impact resistance and deterioration in workability and moldability. Note that n and w in the above characteristic (e) of the terephthalic acid diallyl ester copolymer of the present invention are values determined by the following measuring method. (e) Measurement method for n and w: - Measure and determine by gel permeation chromatography. Using a 150CGPC manufactured by Waters, data is processed using a data module manufactured by Waters, and n and w are calculated. The columns are two 10 ² Å from the Waters Micro Column series,
One each of 5×10 ² Å, 10 ³ Å, 10 ⁴ Å, and 10 ⁵ Å are used, connected in series in this order, and the measurement is performed using tetrahydrofuran as a solvent at a temperature of 25° C. and a flow rate of 2.0 ml/min. First, create a calibration curve. Six types of commercially available standard polystyrene with known number average molecular weights (number average molecular weights are 350,000, 217,000, 92,600, 9,100,
3570, 1790) and diallyl terephthalate monomer (molecular weight 246) to determine their respective retention times. The obtained data are input into the above data module to obtain a calibration curve in which the relationship between number average molecular weight and retention time is approximated by a cubic curve. 20mg of sample copolymer and 20ml of tetrahydrofuran
Approximately 3 ml of the dissolved solution is taken into a special sample bottle and measured using an auto-sampling device. The data is automatically processed in the data module based on the calibration curve created above.
Mn and w are calculated. The peak was divided at 15 second intervals, and the molecular weight of each division point was calculated as Mi,
When the height of the peak is Hi, calculation is performed using the following equations n=ΣHi/Σ(Hi/Mi) and w=ΣMiHi/ΣHi. The terephthalic acid diallyl ester copolymer of the present invention has (f) a molecular weight distribution expressed by the ratio w/n of n and w from 10 to 40. The molecular weight distribution expressed in w/n is approximately 5 to 10 for conventional terephthalic acid diallyl ester polymers, whereas that of the copolymer of the present invention is relatively large. In relation to the above structural features (a) and (b), and subject to the requirements for their combination with other features (c), (d) and (e), they interact with each other. As a result, it has a beneficial effect on improved impact resistance, good flexural modulus, and appropriate curing speed. If the value of w/n is too small (less than 10), the impact resistance will be lowered, and the flow during melting will also be poor during molding, while if it is too large (more than 40), defects will occur in which the curing speed is unduly delayed. Furthermore, the terephthalic acid diallyl ester copolymer of the present invention is distinctive in that it has the features (a) to (f) described above, and is a copolymer that is different from conventional terephthalic acid diallyl ester polymers. However, it is preferable that it further exhibits at least one of the following characteristics (g) to (i). The terephthalic acid diallyl ester copolymer of the present invention preferably has (g) a softening range of 50 to 120°C, preferably about 60° to about 110°C, more preferably about 70° to about
Indicates 100℃. This softening range means that the softening temperature has been relatively shifted to a higher softening temperature side compared to that of conventional terephthalic acid diallyl ester polymers, which was up to about 100°C. The invention copolymer has excellent processability and moldability under the above-mentioned characteristics (a) to (f) and bonding requirements, and is useful for avoiding distortion during curing.
If the softening range is far from the above range and is too small, the moldability will deteriorate and there will be a disadvantage of unreasonable delay in the hardening speed, and if it is too large, the processability will be poor, the moldability will also deteriorate, and the molding distortion will be large. This may cause problems such as In the present invention, the softening temperature is a value determined by the following measuring method. (g) Measurement and determination of softening temperature: - Use a PF61 optical transmission automatic melting point measuring device manufactured by Mettler. Thoroughly crush the sample copolymer in an agate mortar,
Be careful not to leave any gaps in the attached capillary tube, and fill it to a height of about 4 mm. The sample was set in the above apparatus, the temperature was raised from about 40°C at a rate of 0.2°C per minute, and the light transmittance of the set sample was measured.
The measurement results are recorded on recording paper, and a measurement curve as shown in the attached drawing showing the relationship between temperature and light transmittance is obtained. In the figure, the horizontal axis shows temperature and the vertical axis shows light transmittance. Extend straight line XA before melting. Straight line when melting
Extend YF. Straight line part of curve AF during melting
Extend CD to both sides and find the intersections B and E with the two straight lines drawn earlier. Draw a straight line passing through B so as to bisect the area of the triangle ABC thus created, and find the point of intersection B' with the measurement curve. Find the intersection E' in the same way. From the horizontal axis,
Read the temperatures at B' and E', and define the softening range of the sample between B' and E'. The terephthalic acid diallyl ester copolymer of the present invention preferably has (h) a viscosity of a 50% by weight methyl ethyl ketone solution of 80 to 300 centipoise (30°C). These favorable conditions, together with the preferable Brabender melt viscosity properties described in the next item (i), together with the other characteristics of the copolymer of the present invention described above, improve the processability and moldability of the copolymer of the present invention. It also helps to improve the curing speed, maintain an appropriate curing speed, and prevent curing distortion. As mentioned above, the terephthalic acid diallyl ester of the present invention preferably has (i) a Brabender melt viscosity of 250 to 250 as measured by a Brabender plastograph.
2600 m・g, preferably 400 to 2500 m・g, processing time 5 to 65 minutes, preferably 10 to 60 minutes.
It's a minute. In the present invention, the viscosity, Brabender melt viscosity, and processing time are measured and determined as follows. (h) Measurement and determination of viscosity: - Add 15~ of the sample copolymer to a 100 ml Erlenmeyer flask.
Accurately weigh 25 g and dissolve by adding the same weight of methyl ethyl ketone to make a 50% by weight solution. Transfer this solution to an Ubbelohde viscometer, place it in a thermostatic water bath pre-adjusted to 30°C, let stand for 15 minutes, and then measure. Measure the flow time t to the nearest tenth of a second with a stopwatch. Repeat the measurement three times and take the average value. Further, the coefficients of the Ubbelohde viscometer are determined using a suitable standard solution for calibrating a commercially available viscometer. On the other hand, the specific gravity d ³⁰ ₄ of the sample solution is measured using a Geiliussack pycnometer. The desired viscosity η is calculated using the following formula: η=t××d ³⁰ ₄ . (i) Measurement and determination of Brabender melt viscosity and processing time: - Measured using a Brabender Plastograph manufactured by Brabender AG (Germany). The kneading chamber capacity is 50 c.c., and the rotor model is W50H. Add 0.5 g of zinc stearate to 50 g of the sample copolymer, mix well to uniformly disperse, and use the material to be measured. Kneading chamber temperature
Measurements were taken at 130℃ and rotor rotation speed of 22 revolutions per minute.
The change in kneading resistance with respect to kneading time is recorded on recording paper as a torque curve in units of m.g. The measurement is
Continue until the kneading resistance reaches 5000m・g. From the torque curve on the recording paper, read the lowest value of torque and use it as the Brabender melt viscosity.On the other hand, read from the recording paper the time from the end of sample introduction until the kneading resistance reaches 5000 m・g and calculate the processing time. I decide. The structural features of the terephthalic acid diallyl ester copolymer of the present invention have already been described in detail with respect to features (a), (b) and (c). Here, toluene is expressed as
(2) The above formula shown when used as a compound
The part of the (B) structural part in the (A) structure on the opposite side from the monomer unit of formula (2) is a part involved in the polymerization termination reaction or destructive chain transfer reaction, and therefore can have various structures. It cannot be shown with one structure.
According to the studies of the present inventors, for example, several structures such as those shown below exist in a mixed manner. One type is a structure that is generated by coupling the terminal radicals of the formula (B) structural moiety, that is, the formula (B ₁ ) and/or formula (B ₂ ) structural moiety in the formula (A) structure, for example, This includes the following cases. Another type is a structure generated by a hydrogen abstraction reaction by the terminal radical of the structural moiety of formula (B), and includes, for example, the following cases. Still other types include structures in which unsaturated bonds are formed due to a disproportionation reaction between radicals at the terminals of the structural part of formula (B), and include, for example, the following cases. In addition, the terminal radical of the structural part of formula (B) and the formula
(2) A terminal structure resulting from a reaction with a radical generated at one benzyl position of a monomer, an allyl radical generated when the allyl group contained in the terephthalic acid diallyl ester monomer or partial structure abstracts the hydrogen atom at the allyl position. There may be terminal structures produced by similar reactions and other various terminal structures. The terephthalic acid diallyl ester copolymer of the present invention can be prepared, for example, by the method exemplified below.
By selecting specific controlled reaction conditions, the following equation (1) Terephthalic acid diallyl ester represented by
The following formula (2) However, in the formula, R ¹ and R ² each represent a group selected from the group consisting of a hydrogen atom and a lower alkyl group, n represents an integer of 1 to 3, and at least one benzyl position represented by It can be produced by copolymerizing an aromatic hydrocarbon having a hydrogen atom. As already described in detail, the present invention has clarified that such a copolymer can exist, and its characteristics and means of identification. Using these as guidelines, other manufacturing modifications have been experimentally established. It is within the skill of those skilled in the art to employ other manufacturing means. Therefore, it should be understood that the terephthalic acid diallyl ester copolymer of the present invention is not limited to the production mode illustrated below. The terephthalic acid diallyl ester copolymer of the present invention is, for example, as described in detail below in an embodiment using xylene as the compound of formula (2).
It can be produced by reacting a compound of formula (1) and a compound of formula (2) under "cage effect" conditions in the presence of a known organic peroxide or azo compound catalyst. . Production examples will be described in detail below, taking as an example an embodiment in which diallyl terephthalate (DAT) and xylene are polymerized using a di-tert-butyl peroxide (DTBPO) catalyst. Charge xylene into a polymerization tank, and mix the three components diallyl terephthalate (DAT), di-tert-butyl peroxide (DTBPO), and xylene in a molar ratio.
While maintaining the ratio of 2.0 to 8.4:0.5:1, the polymerization operation is carried out under strong stirring while simultaneously and continuously feeding the polymer into the polymerization tank from a nozzle provided at one point in the polymerization zone. The amount of xylene that should be charged into the polymerization tank in advance is 5 times the weight of DAT used in the polymerization reaction.
It is better to have at least twice the weight. The xylene and DTBPO are conveniently mixed in the above ratios before being fed to the polymerization vessel, and the mixture is preferably cooled to below about 5°C. The reason is,
This is to prevent the possibility that DTBPO thermally decomposes to produce tert-butoxy radicals, which extract hydrogen from the methyl group of xylene to produce methylbenzyl radicals, which may then couple. The above nozzle is, for example, a double tube, and the mixture of xylene and DTBPO is passed from the inner tube through the outer tube, which is made to surround the circumference of the inner tube. It is conveniently designed to supply Good results are obtained and it is preferred for the inner tube to be shorter than the outer tube so that the three components are mixed just before being fed into the liquid phase. In order to prevent DAT and DTBPO supplied from the nozzle from escaping into the space of the polymerization tank and disturbing the above ratio, it is desirable to install the nozzle outlet so that it is always in the liquid phase. It is best to use turbine blades or other highly efficient stirring means for stirring, with a circumferential speed of approximately 20 m/min.
It is preferable to stir strongly for at least 1 second. In this example, a polymerization temperature of about 140-170°C is suitable. The boiling point of DTBPO at normal pressure is
Since the temperature is 109°C, the reactor is a closed system in order to keep the temperature sufficiently in the liquid phase and maintain the above ratio. Therefore, DAT and xylene
A high-pressure pump is used to supply each DTBPO mixture. For example, if components with different temperatures, viscosities, and compositions are supplied into a high-temperature liquid phase system and rapidly dispersed in the above embodiment, microscopically, DAT,
The cage effect condition can be realized by dispersing numerous minute "cages" consisting of the three components DTBPO and xylene in the liquid phase. If these components are supplied from nozzles located sufficiently apart, the individual components will simply be dispersed in the liquid phase, making it difficult to achieve the desired cage effect conditions. The same applies when a predetermined amount is prepared at once from the beginning. For example, as described above, by carrying out the reaction under "cage effect" conditions consisting of DAT and xylene, 0.5 mol of DTBPO is thermally decomposed to 1 mol of t.
-butoxy radical is produced, but the radical
In order to control the addition to DAT, the radicals were initially diluted with xylene and
DAT is also preferably cooled to about 15°C in advance to reduce its activity. Thus, through the reaction under the cage effect conditions, the radical quantitatively extracts hydrogen from the xylene in the cage to generate 1 mole of methylbenzyl radical, and this radical has a large ability to add to DAT, so the DAT in the cage is added to the carbon of the allyl group, and polymerization begins. In this way, according to the above manufacturing example, the "basket"
Among them, the methylbenzyl radical first becomes DAT.
Polymerization can be initiated by attacking the monomer. On the other hand, since the inside of the polymerization tank is strongly stirred,
The molecules inside the “cage” are quickly and uniformly dispersed within the system.
Due to the sufficient dilution effect of the large amount of xylene that was dissolved and charged into the polymerization tank in advance, the growth reaction rate of allyl polymerization of DAT monomer becomes extremely slow, and the rate of termination reaction becomes relatively large.
Methylbenzyl radical at its benzylic position
The number of polymer molecules is equal to the number of radicals generated by addition of the allyl group of the DAT monomer and its ₃ C and/or ₃ ' C with a carbon-carbon bond structure. Therefore, the size of the unit chain is
The molar ratio of DAT monomer and DTBPO cannot be higher than that of a unit chain, that is, one xylene molecule.
It is presumed that the reaction can be controlled so that a molecular chain consisting of 3 to 11 DAT monomer units in the carbon-carbon bonded molecular chain portion formed by the allyl group of the DAT monomer unit is generated. In order to obtain a copolymer with the desired composition and structure by adjusting the ratio of each component supplied, first, the hydrogen abstraction reaction from xylene must be carried out quantitatively until the "cage" is destroyed. The temperature in the examples is preferably a high temperature of about 140-170°C. Also
The t-butoxy radicals generated from DTBPO may come out of the "cage" and reduce the initiation efficiency of polymerization.
In order to prevent the DAT ratio from being disturbed, as described above, it is convenient to provide the nozzle at one point. As the polymerization reaction progresses, there are reactions between unit chains, reactions between growing unit chains and already formed unit chains, and as the polymerization reaction progresses, several unit chains react to form a large molecule. The copolymer also becomes involved in the reaction, and at these stages, unreacted allyl groups of the DAT monomer units in the polymer participate in the reaction. In other words, when two unit chains share at least one DAT monomer, the polymer becomes larger. Therefore, depending on which part of the unit chain reacts, it is determined whether the overall structure of the copolymer will extend in a ladder shape or take a round shape with many branches. There is another very important point in forming the copolymers of this invention. In order to make the diallyl terephthalate copolymer into an elongated form, the methylbenzyl radical forms an allyl radical attached to the allyl group of the DAT monomer rather than the allyl group already attached to the polymer, and the xylene The reaction should be controlled so that the bulky radicals generated from one molecule and one DAT monomer (possibly more than one) can serve as a starting point for substantial growth. As is well known, one way to improve impact resistance is to cure the material at an appropriate crosslink density while causing sufficient entanglement in the molecular chains that extend like cotton. It is also known that such so-called macromolecular effects generally appear from a molecular weight of around 5,000. As mentioned above, it is essential to create a polymer that has an essentially elongated structure rather than a thread-like structure in order to improve impact resistance. According to the method of the production example described above, a methylbenzyl radical that is easily added to an allyl radical is generated, and this is first converted to DAT.
By being able to control the reaction to create bulky radicals by adding them to monomers, during the growth of the molecular chain, the reaction occurs preferentially to the allyl group at the end rather than to the sterically hindered interior of the molecular chain. It is assumed that this makes it possible to produce a copolymer with a ladder-like elongated shape. Furthermore, according to the above production example, the system as a whole is
Since the molar ratio of DAT and DTBPO is kept constant, the length of the carbon-carbon bond molecular chain portion, that is, the unit chain formed by the allyl group of the DAT monomer unit of one xylene molecule, is approximately constant on average. can be controlled. The growth of the copolymer according to the present invention is achieved through a process that includes reactions between these unit chains, but if reactions are caused simply stochastically at all positions in the molecular chains, the above-described As shown above, polymers tend to take on a thread-like structure rather than spreading out. Loop-like locations are also likely to form between molecular chains, which promotes gelation. After the copolymerization is completed by supplying a predetermined amount of DAT, DTBPO, and xylene at a predetermined feed rate, the copolymer is separated using, for example, aliphatic hydrocarbons or alcohols and dried. The terephthalic acid diallyl ester copolymer of the present invention, which is a thermosetting resin and has extremely excellent impact resistance, can be obtained. Examples of aliphatic hydrocarbons to be used include hexane and heptane, and examples of alcohols include methanol, ethanol, isopropyl alcohol, and tert-butyl alcohol. Above, one production example has been described in detail along with guidelines for selecting specific controlled reaction conditions for producing the terephthalic acid diallyl ester copolymer of the present invention. Now that the diallyl ester copolymer, its structural characteristics, and identification means have been clarified by the present invention, those skilled in the art can easily experimentally set up various other manufacturing modifications in consideration of the above guidelines. Can be done. The groups R ¹ and R ² of the aromatic hydrocarbon having at least one hydrogen atom at the benzyl position of the formula (2) used to form the terephthalic acid diallyl ester copolymer of the present invention are hydrogen, respectively. The lower alkyl group is selected from the group consisting of atoms and lower alkyl groups, and examples of the lower alkyl group include C ₁ -C ₅ alkyl groups. Examples of such compounds of formula (2) include toluene, ethylbenzene,
n-propylbenzene, isopropylbenzene,
n-butylbenzene, isobutylbenzene, sec
-butylbenzene, n-amylbenzene, sec-
amylbenzene, isoamylbenzene, (2-methylbutyl)-benzene, o-xylene, m-xylene, p-xylene, xylene isomer mixture,
pseudocumene, 1,2-diethylbenzene,
1,3-diethylbenzene, 1,4-diethylbenzene, 1,2-dipropylbenzene, 1,3-
Dipropylbenzene, 1,4-dipropylbenzene, diisopropylbenzenes, p-cymene,
1,2-dibutylbenzene, 1,3-dibutylbenzene, 1,4-dibutylbenzene, 1,2-diisoamylbenzene, 1,3-diisoamylbenzene, 1,4-diisoamylbenzene, 1,2,
Examples include 3-trimethylbenzene. Further, an organic peroxide catalyst used to form the terephthalic acid diallyl ester copolymer of the present invention,
Examples of the azo compound catalyst include the following compounds. Dialkyl peroxides and diaryl peroxides such as di-tert-butyl peroxide, sec-butyl peroxide, tert-butyl-sec-butyl peroxide, and dicumyl peroxide. Diaroyl peroxides and diacyl peroxides such as benzoyl peroxide. Di-tert-butyl peroxalate, tert-perbenzoate
- alkyl esters of percarboxylic acids such as butyl; 2,2'-azobisisobutyronitrile;
2,2'-azobis-(2-methylbutyronitrile), 2,2'-azobis-(2-methylheptanitrile), 1,1'-azobis-(1-cyclohexylcarbonitrile), 2,2' -Azo compounds such as methyl azobisisobutyrate, 4,4'-azobis-(4-cyanopentanoic acid), azidobenzene, etc.; tert
-butyl hydroperoxide, sec-butyl hydroperoxide, tetralyl hydroperoxide, cumyl hydroperoxide, benzyl hydroperoxide, benzhydryl hydroperoxide, decalyl hydroperoxide, acetyl peroxide, cyclohexyl hydroperoxide,
Hydroperoxides such as n-decyl hydroperoxide; Furthermore, compounds easily oxidized by molecular oxygen, in the present invention, terephthalic acid diallyl ester, at least one hydrogen at the benzyl position represented by formula (2) This corresponds to an aromatic hydrocarbon having atoms or the copolymer of the present invention, but if these are oxidized with air or oxygen in advance or during the copolymerization reaction to produce a peroxide, the copolymerization reaction of the present invention can be performed. Can be used satisfactorily as a catalyst. As already mentioned, it is often pointed out that conventional terephthalic acid diallyl ester polymer resins lack toughness, are prone to chipping when dropped while handling molded products, and protruding parts such as ribs are easily damaged. When used as a connector for electronic circuits, there were various complaints in practical use, such as the contact surface with the printed wiring board being easily damaged and the screw being easily cracked when tapped. Furthermore, in recent years, with the miniaturization of electronic devices and components, for example, there has been a demand for narrower spacing between pins of connectors. In addition to soldering, which requires heat resistance, pressure bonding wiring methods have become widespread, allowing the use of thermoplastic resins; however, due to the requirements for dimensional stability, heat resistance, creep resistance, etc. Resin is often used. Therefore, there has been a strong demand in the industry to improve the toughness and impact resistance of diallyl phthalate resins. Conventionally, impact resistance has been compared using the Shalpy and Izod impact values, but although these can be used as a measure for thick walls, the situation often changes when it comes to thin walls. Therefore, the inventors of the present invention decided to mainly adopt a drop weight test using a thin plate, taking into consideration the trend toward miniaturization of parts. As a result of this comparative test under the same conditions, the falling weight impact value of the terephthalic acid diallyl ester copolymer resin of the present invention was about 20 to 30 mm, whereas that of the conventional terephthalic acid diallyl ester polymer resin. ,about
It exhibits the characteristic property of having an unexpected and significantly improved impact resistance of 80 mm or more, later reaching 189 mm as shown in Example 17. Furthermore, in terms of bending strength, while conventional terephthalic acid diallyl ester polymer resins have a bending strength of about 4.0 to 6.3 Kg/mm ² , the terephthalic acid diallyl ester copolymer resin of the present invention has a bending strength of about 6 Kg/mm ² . As mentioned above, as shown in Example 21 later, it exhibits excellent bending strength reaching 7.4 Kg/mm ² . Thus, the terephthalic acid diallyl ester copolymer resin of the present invention has particularly excellent impact resistance, exhibits improved bending strength, and at the same time has low mold shrinkage, heat resistance, creep resistance, and dimensional stability. It has excellent insulation properties, chemical resistance, mechanical strength, and electrical insulation properties, and in particular has excellent insulation performance under harsh conditions of high temperature and high humidity for a long period of time, and resistance to deformation under high temperature and load conditions. It is an excellent thermosetting resin that satisfies or exceeds all the properties of diallyl phthalate resins, such as hardness and dimensional stability, and also has the surprising toughness mentioned above. The terephthalic acid diallyl ester copolymer resin of the present invention may contain fillers, polymerization accelerators, polymerization inhibitors, internal mold release agents, coupling agents, pigments, and other additives as desired. It is possible to improve the molding processability or the physical properties of a molded article by blending them within a range that does not impair the properties of the resin. Examples of fillers that can be used include inorganic and/or organic fillers, and these can be used alone or in combination. The amount used may range from about 1 to about 300% by weight based on the weight of the copolymer resin. Specific examples of these fillers include talc, mica, asbestos, glass powder,
Silica, clay, shirasu, titanium oxide, magnesium oxide, calcium carbonate, alumina, asbestos fiber, silica fiber, glass fiber, silicate glass fiber, alumina fiber, carbon fiber, boron fiber, beryllium fiber, steel fiber, whisker, etc.; organic Examples of fillers include natural fibers such as cellulose, pulp, acrylic fibers, polyester fibers such as polyethylene terephthalate, cotton, rayon, and vinylon. Examples of the polymerization accelerator include metal soaps such as cobalt salts, vanadium salts, and manganese salts of naphthenic acid or octoic acid, and aromatic tertiary amines such as dimethylaniline and diethylaniline. Examples of the amount used include about 0.005 to about 6% by weight based on the weight of the copolymer resin of the present invention. Furthermore, examples of polymerization inhibitors include, for example,
Examples include quinones such as p-benzoquinone and naphthoquinone, polyhydric phenols such as hydroquinone, p-tert-butylcatechol, hydroquinone monomethyl ether, and p-cresol, and quaternary ammonium salts such as trimethylammonium chloride. Examples of the amount used include about 0.001 to about 0.1% by weight based on the weight of the copolymer resin of the present invention. Examples of internal mold release agents include metal salts of stearic acid such as calcium stearate, zinc stearate, and magnesium stearate. The amount used is
Illustrative amounts include from about 0.1% to about 5% by weight based on the weight of the copolymer resin of the present invention. Furthermore, examples of coupling agents include r-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and the like. Examples of the amount used include about 0.01 to about 3% by weight based on the weight of the copolymer resin of the present invention. Examples of pigments include carbon black, iron black, cadmium yellow, benzidine yellow, cadmium orange, red iron, cadmium red,
Examples include pigments such as cobalt blue and anthraquinone blue, and the amount used thereof is about 0.01 to about 10% by weight based on the weight of the copolymer resin of the present invention. As already described in detail regarding feature C, the terephthalic acid diallyl ester copolymer resin of the present invention has an unsaturated group derived mainly from the double bond of the allyl group in the (C ₂ ) structural part by the Wiss method. 45-80 as degree of unsaturation expressed in measured iodine number
It is a prepolymer that can be further cured to become an insoluble and infusible three-dimensional polymer. Accordingly, the copolymer resins of the present invention contain a suitable peroxide, such as dicumyl peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, etc., in an appropriate amount, e.g. Approximately 0.1-6% by weight based on combined resin weight
A thermosetting resin that can be irreversibly cured by mixing and heating the copolymer resin in the following amounts, either in the form of the copolymer resin itself or in the form of a compound containing additives such as fillers as exemplified above. It can be molded into various molded products using various molding methods. In addition to the above, peroxides that can be used for curing the copolymer resin include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, and 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane. peroxyketals such as, hydroperoxides such as cumene hydroperoxide, diaroyl peroxides such as lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxide, peroxycarbonates such as diisopropyl peroxydicarbonate, Examples include peroxy esters such as tert-butylperoxyacetate, tert-butylperoxypivalate, and tert-butylperoxyoctoate, and azo compounds other than organic peroxides such as azobisisobutyronitrile can also be used. can. Examples of such molding methods include a casting method in which a diallyl terephthalate monomer solution of the copolymer resin of the present invention is injected into a mold and hardened, and a method in which the copolymer resin is heated to make it fluid. Injection molding method or transfer molding method in which the material is placed in a mold and heated to harden.
A compression molding method in which the copolymer resin is cured by heating and pressurizing it in a mold, and the copolymer resin is dissolved in a suitable organic solvent and impregnated into a fibrous sheet, and after drying, pressurizing conditions are applied if necessary. Below, a laminate molding method in which the resin is cured in a fibrous sheet, a coating method in which a fine powder or solution of the copolymer resin is applied to a substrate and cured on the substrate, and a solution of the copolymer resin. An example of a molding method is a decorative board molding method in which printing paper or the like is impregnated with the resin, dried, and then cured by heating and pressing on a substrate. During molding, the heating temperature for curing can be exemplified at a temperature of about 120 to about 190°C. or,
When applying pressure conditions, the pressure is approximately 5~
A pressure such as about 1000 Kg/cm ² can be exemplified. The terephthalic acid diallyl ester copolymer resin of the present invention can be used as a molding material in a wide range of fields, either alone or in combination with additives such as those exemplified above, or in combination with other resins and monomers. . For example, connectors, motor commutators, governors, coil bobbins, relays, switches, terminal boards, ignitions, breakers, sockets, binders for sliding resistors, printed wiring boards, encapsulating materials for electronic parts and elements, coil encapsulation, and other light electrical appliances. Electrical and electronic fields such as insulating materials in the heavy electrical field; For example, plastic brake pistons and other mechanical fields; For example, tableware and other daily necessities fields; For example, medical materials field such as trays and containers that require chemical or steam sterilization. It is useful as a molding material in Furthermore, the copolymer is impregnated or applied onto a fibrous sheet such as paper, non-woven fabric, glass cloth, etc. in the presence or absence of a solvent, and the copolymer is pressed and cured onto a wood, paper, metal, or other inorganic substrate, or The pre-cured material is pasted onto the above base material and used in the form of a decorative board for various building materials, furniture/interior items, cabinets, etc.
It is useful for kitchen equipment, vehicle/ship interior materials, and other fields. In addition, if the copolymer is directly impregnated into wood and cured, it becomes a wood-plastic composite (so-called WPC), which can be used in fields such as flooring, edge decking, roofing, building structural materials, and sporting goods. Also, as a laminate made by impregnating and laminating glass cloth or other fibrous sheet structures, it can be used in fields that require various properties at high temperatures and high humidity, such as terminal plates, wedges for motors, insulating collars, slot armor, etc. It is useful for rotating machine-related fields such as coil separators, stationary equipment-related fields such as duct pieces, barriers, terminal plates, operating rods, panels such as switchboards, printed wiring boards, variable cap insulating supports, etc.・It has excellent dimensional stability even under severe humidity changes, and is used in fields that require good mechanical strength, such as radomes, missile blades, rocket nozzles, jet aircraft air ducts, and parts of various chemical equipment. Fields that require chemical properties,
Fields that require weather resistance, chemical resistance, and mechanical strength such as antennas, skis, ski stocks, and fishing rods, other paints, mold materials for other resins, hot stamping resins, UV curing inks, lenses Other optical materials, glass fiber, carbon fiber binder, light, electron beam or X
It can be used in a wide range of applications, including as a resin for resist films in phosphor-fi using wires. EXAMPLES Hereinafter, several examples of the terephthalic acid diallyl ester copolymer of the present invention and its production examples will be explained in more detail with reference to Examples. Examples 1 to 12 Inner diameter 600 mm, internal volume 120, equipped with turbine blade type variable stirrer, double pipe type supply nozzle for monomer and catalyst supply, nitrogen purge port, leak valve, sampling port, thermometer and pressure gauge With jacket
A polymerization tank made of SUS304 was used. The double-pipe supply nozzle for monomer and catalyst supply is installed below the liquid level in the body of the polymerization tank, and the inner diameter of the outer pipe is set to 1.5 mm before entering the polymerization tank to minimize the residence time in the supply piping. I made it shorter. Three such nozzles were installed in preparation for nozzle blockage. A sampling port was also installed in the body of the polymerization tank, making it possible to take samples of the liquid phase using the internal pressure during the polymerization reaction. An oil rotary vacuum pump and a nitrogen cylinder were connected to the nitrogen purge port so that they could be switched as needed. 60 kg of aromatic hydrocarbon (HC) of formula (2) shown in Table 1 below was charged into the above polymerization tank, and the operation of reducing the pressure with a vacuum pump at room temperature and returning to normal pressure with nitrogen gas was repeated three times. After replacing the air in the tank with nitrogen, the pressure was reduced again and the polymerization tank was sealed. The stirrer was started and while stirring at 240 RPM, steam was passed through the jacket to raise the temperature to 140°C. The stirring speed was increased to 720 RPM, and diallyl terephthalate was added from the outer pipe of the double pipe nozzle at the specified speed, and at the same time, di-tert-butyl peroxide (DTBPO) and aromatic hydrocarbon (HC) of formula (2) were added. were mixed in advance at a molar ratio of 0.5:1 and supplied to the polymerization tank at a predetermined rate using a pump with a discharge pressure of 70 kg/cm ² . In addition, only in Example 5, peroxide di-
Dicumyl peroxide was used instead of tert-butyl.
During this time, the steam was adjusted so that the temperature of the polymerization tank was maintained at 140°C. Note that the formula (1) diallyl terephthalate (DAT) to be supplied is kept at 15℃, and the mixture of di-t-butyl peroxide and aromatic hydrocarbon is kept at 5℃.
The pipes leading to the polymerization tank were kept cool. The polymerization tank pressure was 0.3 to 2 Kg/cm ² G. Once the specified amount of diallyl terephthalate, aromatic hydrocarbon, and di-tert-butyl peroxide has been supplied, the steam is turned off and the stirring speed is reduced to 240 RPM.
Then, cooling water was passed through the jacket to cool it. After cooling to around room temperature, the leak valve was opened to return to normal pressure, and the polymerization reaction was completed. During the polymerization reaction, samples were appropriately taken from the sampling port, and the reaction was monitored using refractive index and GPC. The feed rates and amounts of diallyl terephthalate, aromatic hydrocarbon and di-tert-butyl peroxide are shown in Table 1 below. The volatile components of the polymerization reaction solution obtained above were distilled off using a thin film evaporator, and the amount of unreacted aromatic hydrocarbons in the evaporation residue was calculated based on the total of the copolymer and unreacted diallyl terephthalate. The ratio was set to 0.3:1 by weight, and the evaporation residue was then added dropwise to a stirring tank containing methanol in an amount 5 times the weight of the supplied diallyl terephthalate while stirring to precipitate a copolymer. The precipitated copolymer was thoroughly washed with the same amount of methanol, filtered, dried, and pulverized to obtain a powdery copolymer. The yield and physical properties of the copolymer are shown in Table 1 below. Comparative Example 1 Polymers were produced in exactly the same manner as in Examples 1 to 12, except that benzene was used instead of the aromatic hydrocarbon of formula (2). The results are shown in Table 1 below. Comparative Example 2 Diallyl terephthalate 10Kg, peroxide di-tert-
A mixture of 25 g of butyl was reacted at 120° C. for 2 hours with stirring, and after cooling, the polymer solution was dropped into 60 kg of methanol with stirring to precipitate a polymer. The polymer was washed three times with 60 kg of methanol each time to form a powder, which was then filtered, dried, and pulverized to obtain a diallyl terephthalate homopolymer. The physical properties of the obtained polymer are shown in Table 1 below.

【table】

【table】

[Table] Examples 13 to 24 and Comparative Examples 3 to 4 (a) Preparation of unfilled compound Take 1 kg of each of the copolymers obtained in Examples 1 to 12, add 20 g of dicumyl peroxide, and mix thoroughly beforehand. , roll kneaded. Front roll temperature 90~100
The mixture was kneaded for 5 minutes at a rear roll temperature of 60 to 80°C, taken out from the rolls into a sheet, allowed to cool, and then coarsely crushed using a Henschel mixer. (b) Compression molding of unfilled compound Take 20-30g of the unfilled compound obtained above,
A nearly disc-shaped tablet with a diameter of 50 mm and a thickness of 10 mm was made using a mold using a manual press, and after preheating to approximately 80°C with a high-frequency preheater, the compression molding mold was immediately adjusted to the specified temperature. Place it in the center of the mold cavity and use an automatic press to press the mold at a temperature of 160℃ and a pressure of 100℃.
The product was molded at Kg/cm ² for a predetermined time to obtain a disc-shaped molded product with a diameter of about 100 mm and a thickness of about 2 mm. The compression molding time and the physical properties of the molded product are summarized in Table 2. The method for measuring the physical properties of the molded product is as described after Table 2. For comparison, unfilled compounds were prepared in the same manner as in Examples 13 to 24 above, except that the polymer obtained in Comparative Example 1 was used, and compression molded in the same manner.
The results of a similar test are shown in Table 2 (Comparative Example 3). Similarly, for comparison, the same procedure as above was carried out except that the polymer obtained in Comparative Example 2 was used, and the results are shown in Table 2 (Comparative Example 4).

【table】

【table】

[Table] Methods for testing physical properties of molded products; - (1) Rockwell hardness: Measured at room temperature using a Rockwell hardness meter (M scale), and is expressed as the arithmetic mean value of three measured values. (2) Thickness of test piece: Measure the thickness using a micrometer at the center of the molded product sample. (3) Specific gravity: Cut out three test pieces of any shape from the molded product and use them. The weight (a grams) of each test piece is actually measured. The weight (c grams) of the jig for hanging the test piece in water is actually measured. Next, the test piece is suspended with a jig and the total weight (b grams) in water is actually measured and calculated using the following formula. Specific gravity=a/(a-b+c) The measurement was carried out at 25±0.5°C, and the arithmetic mean value of three test pieces is shown. (4) Dimensional shrinkage rate: Measure the diameter of the molded product sample using a micrometer, find the difference from the mold cavity diameter (100 mm), divide by the mold cavity diameter, and multiply by 100 to show the value. . (5) Bending strength: Test piece: 6 test pieces with a width of about 25 mm from 3 molded products.
Use pieces cut out with a diamond cutter. Testing machine: TENSILON/UTM-111-500 (manufactured by Toyo Baldwin) Measurement conditions: Load cell 50 kg, support width 60 mm, crosshead speed 1 mm/min Calculation is based on the formula described in JIS K6918, and the arithmetic mean value of 6 points is shown. (6) Falling weight impact value: 36 test pieces were cut out from two molded products using a diamond cutter and subjected to measurement. The test machine used was a Dupont falling ball tester (load 500g, flat support, striking center/2 inch radius).
Determine the 50% fracture height using the mode method (reference:
JIS K7211). (7) DSC reaction rate: The calorific value of the test sample obtained by finely pulverizing the molded product material and the unfilled compound before molding was measured using a differential scanning calorimeter (PerkinElmer
DSC-1B) and calculated using the following formula. DSC reaction rate (%) = (A-B)/A×100 In the formula, A is the calorific value of the unfilled compound (cal/g) B is the calorific value of the finely pulverized molded product (cal/g) (8) Boiling Water absorption rate: Determined according to JIS K6918, except that the test specimen size is a disk test material with a diameter of 100 mm and a thickness of 2 mm. (9) Heat resistance: Tested using three molded products that were left in a constant temperature bath at 150°C for 2 hours and then left to cool in a desiccator. The initial weight of each molded product test piece is actually measured. Next, these test pieces were left in a constant temperature bath adjusted to 240°±2°C for an appropriate period of time, and then allowed to cool in a desiccator, and the weight of each piece was actually measured. At this time, 3
The average weight loss of the test specimens is 10% of the initial weight.
If not, repeat these specimens.
After leaving it in a constant temperature bath at 240°±2°C for an appropriate time,
Ask for weight loss again. This operation is repeated until the average weight loss of the three test pieces reaches 10% of the initial weight, and the total number of days required for this test is determined and shown. (10) Electrical properties: (a) Volume resistivity Performed according to JIS K6918. (b) Dielectric constant The thickness of the test piece is 2 mm, and JIS
Perform according to K6918. (c) Dielectric loss tangent Using the same test piece as in (b) above, JIS
Perform according to K6918. (d) Dielectric breakdown strength Conducted according to JIS K6911 (short time method). (E) Arc resistance JIS except that the test piece thickness is 2 mm.
Perform according to K6918. Examples 25-26 (a) Preparation of full compound 1 kg of each of the copolymers obtained in Examples 2 and 4 above was taken, blended as shown below, and unfilled as described in Examples 13-24 above. A full compound was prepared in the same manner as the compound preparation. Copolymer 100 parts by weight Short glass fibers * 60 Calcium carbonate 40 Dicumyl peroxide 2 Calcium stearate 1 Methacryloxysilane 0.6 Hydroquinone 0.01 * Manufactured by Asahi Fiberglass (b) Compression molding of full compound The methods, conditions, and methods for measuring physical properties are the same as for the unfilled compounds described in Examples 13 to 24 above. The compression molding time and the physical properties of the molded product are summarized in Table 3 below.

【table】

[Table] Example 27 The full compound prepared in Example 26 was injection molded, and the physical properties of the molded product were measured. The injection molding conditions are as shown below. Model: Mini Super 60 (each machine manufacturer) Number of injection molded products JIS bending strength test piece: 1 piece Impact strength test piece: 1 piece Heat deformation temperature test piece: 1 piece Mold temperature (fixed side) 170℃ (movable side) 170℃ Cylinder temperature Front 100℃ 〃 Rear 40℃ Clamping pressure 1300Kg/cm ² Injection amount 105c.c. Injection pressure 800Kg/cm ² Injection pressure holding time 15 seconds Injection time 3 to 4 seconds Screw rotation speed 85 revolutions per minute Curing time: 90 seconds The physical properties of the obtained molded article are shown in Table 4 below. The physical properties of the injection molded product were measured as follows. Bending strength: Sharpie according to JIS K6918 Impact strength: Same as above Heat distortion temperature: Same as above

【table】 [Brief explanation of drawings]

The accompanying drawing is a graph showing the temperature-light transmittance relationship used to determine the softening temperature of the copolymer of the present invention.

Claims (1)

[Claims] 1. The following formula (1) Terephthalic acid diallyl ester represented by and the following formula (2) However, in the formula, R ¹ and R ² each represent a group selected from the group consisting of a hydrogen atom and a lower alkyl group, n represents an integer of 1 to 3, and at least one benzyl position represented by Derived from an aromatic hydrocarbon having a hydrogen atom, the following formula (3) and the following formula (4) A terephthalic acid diallyl ester copolymer having a repeating unit of (a) one monomer unit of the formula (2) at the end of the monomer unit of the formula (1), and one monomer unit of the formula (1) at the benzyl position; ) has a carbon-carbon bond structure with the allyl group of the monomer unit and its ₃ C and/or ₃ ′ C, and (b) the carbon formed by the allyl group of the monomer unit of formula (1) in the copolymer. - the formula of the carbon-bonded molecular chain moiety;
(1) The number of monomer units is 3 to 11, (c) the degree of unsaturation expressed as an iodine number measured by the Wijs method is 40 to 85, and (d) the true specific gravity at 25°C is 1.20. -1.25, (e) the polystyrene equivalent number average molecular weight (n) measured by GPC (gel permeation chromatography) method is 4000 to 10000, and the weight average molecular weight (w) is 70000 to 200000; and (f) a terephthalic acid diallyl ester copolymer, characterized in that the molecular weight distribution expressed by the ratio w/n of n and w is 10 to 40. 2. The terephthalic acid diallyl ester copolymer according to claim 1, wherein the copolymer (g) has a softening range of 50° to 120°C. 3 The copolymer has a viscosity of (h) a 50% by weight methyl ethyl ketone solution of 80 to
300 centipoise (30°C), the terephthalic acid diallyl ester copolymer according to claim 1 or 2. 4. Claims 1 to 3, wherein the copolymer (i) has a Brabender melt viscosity of 250 to 2,600 m·g as measured by a Brabender plastograph, and a processing time of 5 to 65 minutes. The terephthalic acid diallyl ester copolymer according to any one of the above.