JPH06504305A - Arylcyclobutene-terminated carbonate polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Arylcyclobutene-terminated carbonate polymer The present invention It concerns new carbonate polymers with lylcyclobutenes. child Polymer compositions such as molded products, composite or mixed materials and sheets or fibres. Suitable for manufacturing extrusion molded products such as lums.

Combining the physical properties of carbonate and other engineering thermoplastics Many efforts have been made to improve it. For example, US Patent 4. 708. 9 No. 94 has an aromatic group in the resin as described above and a reactive arylcyclobutene. along the polymer backbone by alkylating or acrylating molecules that Reactive aryl cyclobutenes are randomly introduced in a pendant manner. It teaches about the incorporation of cyclobutene. The resin thus produced is Cross-linked and hardened by continuous heat treatment, making it more resistant to solvents and heat becomes. Unfortunately, however, random and uncontrolled crosslinking throughout the polymer backbone Materials with give fruit.

In U.S. Patents 4,795.827 and 4,825,001, polymer or other amino-reactive functional molecules to add a hecyclobutane group. Cyclobutareneketoaniline has been used for this purpose. However, among these The composition of carbonate polymers with cyclobutene ends has not been reported. do not have. Furthermore, polymers with such monomer caps or ends are Due to the thermal instability of the resulting carbamate bonds, typical thermoforming engineering However, it cannot be sufficiently stable as an operating system.

Under these circumstances, one aspect of the present invention is strength, solvent resistance, heat resistance, and thermal stability. The purpose of the present invention is to provide a carbonate polymer that has desirable properties such as properties. Main departure According to the carbonaceous polymers with low, low (both average degree of polymerization of 2 and terminal arylcyclobutene) A method for producing a coated polymer is shown. Another embodiment of the invention has a degree of polymerization of 2 to 100. 0.01 per mole of such carbonate polymer and polyhydric compound with Carbonate polyamide polymerized with 1 mole of terminal arylcyclobutene-containing compound from Including mar.

Another aspect of the invention is that it has a terminal arylcyclobutene moiety; Arylcyclobutene compound chain termination, preferably less per polymer molecule Both of the above carbonate polymers have an average of two terminal arylcyclobutenes. be. A further aspect of the present invention is that the carbonate polymer has a terminal aryl group. with robene and without complete arylcyclobutene compound chain termination. be. Preferably, in the production of the polymer, a fully arylcyclobutene compound one arylcyclobutene chain compound and an additional singular or is a polymer that uses multiple chain termination reagents. In this case an additional chain stop Use 0.01 mole of arylcyclobutene chain termination compound per mole of reagent is desirable.

The carbonate polymer according to the invention is commonly used in carbonate polymer resins. Current technology allows for easy handling and melt processing, and Under crosslinking conditions, physical properties such as heat resistance, solvent resistance, strength, and thermal stability can be improved. This results in a molded product with improved combination. carbonate poly per polymer chain Depending on the molecular weight of the mer and the number of arylcyclobutenes, the cross-linked or branched properties of carbonate polymers can be improved or optimized. polymer Carbonates with two or more terminal arylcyclobutenes per chain Polymers and carbonate polymers with a low degree of polymerization before crosslinking are Good mechanical properties similar to linear high molecular weight thermoplastic carbonate polymers in many respects. While providing molded or tangible products with properties similar to those of low molecular weight thermosets, It is extremely easy to handle. Up to 2 arylcyclobutenes per polymer chain Carbonate polymers with branched carbon units have better melt processability. can be used to obtain nate polymers.

Carbonate polymers are well known in the literature and can be produced using widely known techniques. It can be prepared. Generally speaking, carbonate polymers are divalent phenolic polyhydric compounds such as alcohols and phosgene, haloformates or diphenyl carbon one or more carbonate esters, such as Can be prepared from polyvalent compounds. Carbonate polymers are these raw materials Select an appropriate polymerization method from known interface, solution, and melt polymerization methods using It can be prepared with

Such carbonate polymers generally have repeating structures such as those represented by formula l. Here, n is the number of polymerizations, A is the residue of a polyvalent compound (both radicals with divalence, (-) is the valence and number of A that connects the carbonyl moiety shown in the formula, ■ is 1, It is an integer greater than 1 or 1. Generally, A is mainly a residue of a divalent compound (V is 1) be. However, when the purpose is a branched polymer, A is trivalent or trivalent at low levels. can have the residue of a tetravalent compound (V is greater than 1). Divalent phenol By using aromatic carbon, the most typical carbonate polymer, -bonate polymer is obtained. Carbonate polymer molecules are usually monovalent compounds Alternatively, the terminus is formed by the residue of another monofunctional chain-terminating compound.

Such carbonate polymers are generally represented by the chemical formula (2).

Here, T is independently a monovalent compound with or without an arylcyclobutene group. or the chain-terminating end of another monofunctional chain-terminating compound, where q is preferably 0 or The average number of polymer branches per polymer molecule is in the range 0.05. and( If a branched polymer is desired, q should be in the range 0.01 to 0.05. is desirable.

The types of aromatics available on the market today and most frequently used in thermoplastic molding applications. In aromatic carbonate polymers, n is typically 30 to 315; The average molecular weight of the aromatic polycarbonate is between 20,000 and 200,000. Become. For example, “polycarbonate”, Encydopedia of Poly mer 5science and Technology Vol 11. .

See p. 648 (1987). However, the terminal arylcyclobutene group According to the invention, in which the carbonate polymer is formed before crosslinking, n is advantageously can take values from 2 to 100. This is for example aromatic carbonate It means that the molecular weight (uncrosslinked) of the polymer is between 500 and 65,000.

Generally speaking, the degree of polymerization of a particular carbonate polymer resin according to the present invention Determined by the average number of terminal arylcyclobutenes per mer molecule. per chain Carbonate polymers with two or more terminal arylcyclobutene groups are , has an extremely high degree of cross-linking, rapidly increases the effective molecular weight, and exhibits desirable physical properties. Start giving. Such polymers require only a low degree of polymerization before crosslinking I don't. Branched carbonate polymers have two terminal aryl cyclones per chain. Robene units within the range generally desired for branched carbonate polymers It can be prepared from carbonate polymers with molecular weights.

Therefore, the degree of pre-crosslinking of the polymerization for the carbonate polymers according to the invention is: You can conveniently choose from a relatively wide range. However, it is small (both 2 and desired). preferably greater than 2, more preferably at least 2.5, most preferably less than is also 3. The degree of pre-crosslinking in the polymerization of carbonate polymers according to the invention is generally up to 50, preferably 35 or less, more preferably 30 or smaller, most preferably 20 or smaller.

For aromatic carbonate condensation polymers, these degrees of polymerization are well-known as shown below. It can be calculated and claimed according to the Flory (F l o r y) formula. Ru.

n=(1+r)/(1+r-2pr) r=Xa/(Xa+2Xt) where n is degree of polymerization, r is the molar ratio of reactive groups, p is the degree of reaction progress, and Xa is divalent chain elongation. The mole fraction of the compound, Xt, is the mole fraction of the monovalent chain-terminating compound. P.

J, Flory, “Pr1nciples of Polymer Chemi stry"Cornell Univ, Pr5s, Ithaca, New Y.

See rk, p. 92 (1953).

Two preferred polyhydric compounds used in the production of aromatic carbonate polymers Nols may contain one or more aromatic rings, and each A carbonate precursor compound whose hydroxyl group is directly bonded to an aromatic carbon atom. Even if it contains two or more hydroxyl groups as functional groups, it is reactive with good.

A typical dihydric phenol is 2,2-bis-(4-hydroxyphenyl)-propylene. Bread (“Bisphenol A”); Hydroquinone; Resorcinol; 2,2- Bis-(4-hydroxyphenyl)-pentane; 2,4'-dihydroxydif phenylmethane: bis-(2-hydroxyphenyl)-methane; bis-(4-hydro bis=(4-hydroxy-5-nitrophenyl)- Methane; 1,1-bis(4-hydroxyphenyl)-ethane; 3,3-bis-( 4-hydroxyphenyl)-pentane; 2,2'-dihydroxydiphenyl; 2゜6-hydroxynaphthalene; bis-(4-hydroxyphenynolysulfate) 2,4'-dihydroxydiphenylsulfone; 5'-chloro-2,4 '-dihydroxydiphenylsulfone; bis-(4-hydroxyphenyl) -diphenyldisulfone; 4,4'-dihydroxydiphenyl ether; 4, 4'-dihydroxy-3,3°-dichlorodiphenyl ether; and 4,4 °-Dihydroxyl 2,5-diethoxydiphenyl ether. Desirable power The carbonate polymer contains dihydric phenol, preferably bisphenol, as a polyhydric compound. Prepared using Tool A.

In addition to the preparation of carbonates and homopolymers using a single polyhydric compound in the process, I would like to prepare carbonate copolymer or polyester carbonate. Sometimes two or more polyhydric compounds, or glycerol, hydroxy A combination of a polyester with a di-terminus or a dibasic acid and one polyvalent compound can be adopted. Carbonate copolymers according to the invention have a Preferably 20 or less, more preferably 10 or less, most preferably 5% or less. It contains a ter bonding group. The carbonate polymer according to the invention is a polyvalent Insofar as the compounds are used, they essentially contain one or more aromatic rings, and two or more having a direct bond with an aromatic ring carbon atom as a functional group. Most preferably, it consists of a dihydric phenol containing a hydroxy group. terminal aryl group Randomly branched carbonate polymers that may have clobutene moieties The trivalent and /or trivalent and/or tetravalent phenol, as in the example of tetravalent phenol Compounds can be used. Polymers with random branches used in the present invention Carbonates are well known to those skilled in the art and are described in U.S. Patent No. 3,544,514. In the presence of trivalent and/or tetravalent compounds as exemplified in It is prepared by reacting substances with phosgene.

Carbonate esters are used as carbonate precursors in polymer production reactions. If possible, the material may be exposed to temperatures of 100°C or higher for 1 to 15 hours. Perform a reaction. Under these conditions, polyhydric compounds using carbonate esters A transesterification reaction occurs between Transesterification requires 10 to 100 millimeters of mercury. Proceeds favorably under reduced pressure of meters.

All or part of the backbone chain of the carbonate polymer prepared by the above method is It is then given an arylcyclobutene end. terminal arylcyclobutene As an exception, substances that cause gelation or deterioration of physical properties may irregularities along the polymer molecular backbone that have a detrimental effect on the properties of the polymer. to avoid unharmonious (pendant-like) distribution of arylcyclobutenes in desirable. The arylcyclobutene moiety of the carbonate polymer according to the invention is It is preferable that it basically consists of terminal arylcyclobutene, and more preferable is It has no arylcyclobutene bonded to the skeleton at any point other than at the end. general In other words, a carbonate polymer with arylcyclobutene ends has the following chemical formula: %formula% Here, B is a carbonate polymer, and Ar is an electron-withdrawing substituent or an electron-donating substituent. The carbon atom represented by C is the carbon atom of the aromatic group. Bonded to the carbon atom adjacent to the elementary atom, each R is independently hydrogen, electron withdrawing substituent or electron-donating substituent, X is an integer of 1 or more, y is 1 or an integer greater than 1°, preferably 1°, for example, benzocyclobutene according to the present invention. The functionalized carbonate polymer is represented by the following chemical formula (1).

Here, P is a carbonate polymer, R1 is each independently hydrogen, an electron-withdrawing substituent or an electron donating substituent, 2 represents an integer of 1 or more. Chemical formula above■ , there is no pendant carbonate polymer and R is always hydrogen. Benzocyclobutene is also bicyclo[4,2,0]-octa-1 ゜3,　5-) It is called Lien.

Terminal aryl chains on all or some backbone chains of carbonate polymer molecules The addition of a robene moiety is an aryl chain in the polymerization reaction of carbonate polymers. Use of chain termination compounds functionalized with robene or existing carbonate points Provide appropriate functionality to react with the reactive moiety present at the remer end. achieved by a number of techniques, including the use of arylcyclobutene compounds be done. Compounds suitable as chain termination compounds in carbonate polymerization processes is well known in the literature. Similarly, methods for preparing arylcyclobutene-containing molecules 4,540.763 and 4,708,994. It is known from the literature.

The terminal arylcyclobutene moiety to the carbonate polymer according to the invention is The use of lylcyclobutene-functional chain termination compounds ensures efficient Can be easily implemented. In such compounds, the arylcyclobutene moiety reacts with the elongating carbonate polymer molecule, but such a molecule terminates there. exists inside. For example, even a single acyl chloride or hydroxy functionality First, arylcyclobutene-containing molecules are preferred for carbonate polymerization reactions. used. For example, in U.S. Pat. No. 4,540,763, acid chloride functionality and and hydroxy-functional arylcyclobutene compounds have been described. hydroxy Lloyd et al., Tefrahed, which describes benzocyclobutane. ron, vol, 21. pI), 2281-2288. See also (1965) Do it.

Hydroxybenzocyclobutene and especially 4-hydroxybenzocyclobutene is used in the preparation of carbonate polymers according to the invention. desirable Chain termination compound functionalized with arylcyclobutene. 4-hydroxy Benzocyclobutene is also 3-hydroxybicyclo[4,2,0]-octa- It is called 1,3,5-triene. Hyde in hydroxybenzocyclobutene Roxy moieties are highly reactive and desirable in carbonate polymerization reactions. level of terminal cyclobenzobutene.

Arylcyclobutene chain termination compounds and other carbonate points used specific properties by controlling the total and relative amounts of chain-terminating compounds The concentration of arylcyclobutene groups in carbonate polymers with The molecular weight of the nate polymer can be determined optimally. In this way, the chain The total concentration of stopping compounds is such that the Flory set for this calculation is reproduced. The chain length of the carbonate polymer is determined statistically. arylcyclobutene chain The amount of terminating compound relative to other chain terminating compounds is, on average, What percentage of the topolymer terminates with arylcyclobutene and thus forms It will determine how much branching there will be.

If complete arylcyclobutene chain termination of carbonate polymers is desired, , it is clear that the use of any other chain-terminating compounds should be avoided.

For linear carbonate polymers, complete arylcyclobutene chain termination is , the polymer molecules are terminated with arylcyclobutene moieties at both ends, and a cross-linking reaction is carried out. This means providing a polymer with a completely crosslinked structure. Straight chain This state of the polymer corresponds to the chemistry shown above when X or 2 are each 2. Represented by the formula ■ or ■. It has a relatively low degree of polymerization and has a relatively low degree of polymerization. Carbonate polymers with full chain termination have extremely low initial melting before crosslinking reactions. Although it has viscosity, sufficient strength, solvent resistance, and heat resistance can be easily obtained by crosslinking. Suitable for cases where processable polymers are required.

Branched carbonate polymers are branched compounds with three or more hydroxyl groups. It can also be prepared by use. In this case, when V is 2 or 3, Corresponds to Formula I above. In this case, chain-terminating arylcyclobutene compounds and Molecular weight and relative concentrations of chain-terminating compounds and other chain-terminating compounds - Luciclob To give the theoretical value needed to give the percentage of chain ends with ten ends, can be determined.

The molecular weight before the crosslinking reaction is relatively low (and the arylcyclobutene termination group Carbonate polymers with fully terminated ends may be used if the molten polymer has a relatively large Applications where quick and easy pouring into the formwork is required, such as complex molds. For example, it is suitable for and cross-linking reaction, the product formed has good quality in terms of strength and other properties. I come to do it. A high degree of crosslinking is easily obtained and at the same time relatively high strength (heat and Easily processable polymers that provide moldable polymers that are highly resistant to solvents. It is quite unexpected that this can be obtained.

Hydroxyl or acyl chloride aryl cyclobutene mono in interfacial polymerization When using carbonate polymers to obtain fully terminated polymers, the required carbonate polymer In order to obtain the molecular weight of the polyhydric compound, it is necessary to It has been found suitable to use arylcyclobutene compounds of

The desired molar ratio of arylcyclobutene compound per mole of polyhydric compound is small (both 0.02, more preferably less (both 0.03, most preferably 0. It is 1. Regarding the maximum limit, aryl per mole of polyhydric phenol compound It is necessary that the molar ratio of the cyclobutene compound is less than or equal to 1. preferably equal to or lower than 0.99, more preferably 0.5. It is equal to or lower than.

For example, before polycarbonate such as hydroxybenzocyclobutene, phosgene, etc. Dihydric phenol compound moiety of dihydric phenol such as precursor substances and bisphenol A The interfacial polymerization reaction was performed using a molar ratio of hydroxybenzobutene of 1 mole per mol. When manufacturing carbonate polymers, measurements are taken using the flowry set described earlier. Based on the calculated dihydric phenol compounds, and determined before the crosslinking reaction of the polymer. The degree of polymerization obtained is 2. Using these compounds, fully arylcyclobutene When producing a carbonate polymer terminated by 0.03 mole of hydroxybenzocyclobutene per mole of phenol Can be used.

As mentioned above, one embodiment of the present invention is that all ends of the polymer chain are Contains polymers that are not terminated with cyclobutene. The arylcyclobutene part is Because it reacts with many other arylcyclobutene moieties upon activation. , the resulting carbonate polymer is a combination of arylcyclobutenes that have reacted with each other. A branch will be formed around the point. via arylcyclobutene reaction This partial cross-linking (i.e., branching) of the carbonate polymer allows for the desired It has previously been found that branched carbonate polymers can be obtained.

In this embodiment of the invention, a suitably reactive arylcyclobutene is used as the reactive end. aryl compound in a polycarbonate polymerization reaction or more preferably in a polycarbonate polymerization reaction. Using a chain-terminating compound with one or more other chain-terminating compounds It will be done.

Trees that use arylcyclobutene moieties to perform branching and are available today. Preparation of aromatic carbonate polymers for applications where fats are used For, branching trees with molecular weights in the range of 16,000 to 65,000 It is desirable to obtain fat. Such resins generally contain Chain termination compound (arylcyclobutene) in an amount ranging from 0.04 to 0.01 mol etc.). Amounts of chain termination compounds in this range 0.01 to 0.05 per polymer molecule, as a typical example. Branched molecules can be used with arylcyclobutenes and other chain-terminating compounds. Determined by the equivalent amount of something.

For example, to obtain a notable effect of branching, other chain terminator models must be used. at least 0.01 mole of arylcyclobutene chain termination compound per molecule, preferably preferably 0.03 mole, more preferably 0.05 mole of arylcyclobutene chain termination. Terminating compounds can be used per mole of additional chain terminator. generally desirable To obtain carbonate polymers with large branches but not completely crosslinked, , up to 0.5 mole of arylcyclobutene chains per mole of additional chain-terminating compound terminating compound, preferably up to 0.3 per mole of chain terminating compound, more preferably using 0.2 mole of arylcyclobutene compound per mole of chain-terminating compound. can be done.

The cyclobutene ring of the arylcyclobutene moiety exposes the functionalized polymer to sufficient heat The ring can be opened by Typically 200°C to 300°C for ring cleavage. heating is sufficient. Although copper salt catalysts may reduce the required temperature, , no polymerization solvent or catalyst is required. Very short waves, infrared rays, ultraviolet rays, electron beams and Irradiation with electromagnetic radiation, such as gamma irradiation, can also be used to cleave the ring. , thermal radiation is the more recommended method due to its availability.

Carbonate polymers according to the invention can be used with other polymers, including blends with polyesters. It can be used by mixing or combining with a mer resin. Furthermore, the carb of the present invention fillers (i.e. glass fibers), pigments, dyes, and antioxidants. inhibitors, heat stabilizers, ultraviolet absorbers, mold release agents, impact modifiers, and other forces - Bonate poly Additives commonly used in mer compositions can be added.

As can be seen in Table I, which shows the experiments described below, terminal cyclobutenes are extremely relatively low molecular weight carbonate polymers with a good combination of physical properties. Giving is truly amazing.

According to the following method, benzocyclobutene (“BCB”) with a molar specific gravity of 0.6 or more Experimental number to prepare carbonate polymers with high levels of benzocyclobutene Preparation method A from Nos. 2 to 9 was carried out.

Glass reactor with mechanical stirrer, baffle, thermometer, and pH meter pH electrode connected to, liquid inlet tube, gas inlet tube, 50 weight percent sodium hydroxide Washer containing an aqueous solution of thorium and 1% triethylamine by weight, phosgene wash Attach the gas outlet pipe connected to the blower. This reactor has 68.5 weight parts ( Bisphenol A, 2.16 parts by weight (0,018 moles) Parts) 4-hydroxybenzocyclobutene (BCB-OH), 360 weight Add parts water and 24040 parts by weight chloromethane.

While stirring the reaction solution, add 48 parts by weight (0.6 mol parts) of sodium hydroxide. Add 50 weight percent aqueous solution, then add 37 weight parts (0,375 mole parts) Add the gaseous phosgene of 1) at a rate of 1 part by weight per minute. Maintain pH 12.5 Continue adding as much sodium hydroxide as necessary to achieve this. For addition of phosgene Then 51515 parts by weight chloromethane and 0. 3 weight parts (Morva -1% triethylamine is added. The reaction solution was heated for 20 minutes. By stirring, the bisphenol A polycarbonate with dinzocycloptene ends is generated. Add 9 weight percent phosgene to the mixture to lower the pH to 7. Ru.

The polymer solution is washed with IN hydrochloric acid and water to separate the polymer.

The molecular weight of the polymer was determined by gel permeation chromatography, and the average molecular weight ( Mw) 18.190 was obtained. By liquid chromatography analysis of the residual reaction solution, This showed that 4-hydroxybenzocyclobutene had completely reacted. did Therefore, before crosslinking, the produced polycarbonate has a bisphenol A mole ratio of The degree of polymerization was determined to be 27 with 0.06 mole of benzene clobutene. .

This material was compression molded at 585°F (307°C) and completely dissolved in dichloromethane. This results in an insoluble crosslinked polymer composition-1. Differential scanning calorimetry analyzes the glass transition temperature ( Tg) was 1.65°. This composition is shown below as Experiment 2 in Table I with other physical properties. Shown with properties.

Using the method previously described, a wide range of A series of arylcyclobutenes with molecular weights in the range and high arylcyclobutene concentrations. A carbonate polymer with terminal ends was prepared. As shown in Table 1, Table 1 is the ratio of the mole amount of hydroxybenzocyclobutene to 80 moles of bisphenol. is shown as "BCB molar ratio". As seen in Table 1, the amount of BCB By varying the polymer composition and molecular weight as indicated. Table shows molecular weight and the molecular weight (Mw and Mn), degree of polymerization (n) and multivalency of the resulting polymer. The correlation with the molar ratio of arylcyclobutene to compound is shown. Table I is Additionally, desirable property combinations of the resulting crosslinked polymer compositions are also indicated.

Following a similar procedure described below, BCB molar ratio of 0.03 and lower B ( “Carbonate polymers with B molar ratio, higher BCB molar ratio and higher molecular weight - Prepare. Preparation method B of Experiment 1 was performed. 68.5 weight parts for reactor (0,3 molar parts) of bisphenol A and 36 molar parts of water were added. .

While stirring, add 53 weight parts (0.66 mole parts) of sodium hydroxide to 50% Added in the form of an aqueous solution, followed by 38 parts by weight (0.39 mole parts) Add Sugen one weight part per minute. Then 210 parts by weight of dichlorometh and 1.08 parts by weight (0,009 mole parts) of 4-hydroxybenzo. Add cyclobutene (BCB-OH) and stir the mixture for 2 minutes. p of mixed liquid H can be reduced to 12.5 by adding sodium hydroxide in the form of a 50% aqueous solution. 36060 parts by weight chloromethane and 0.10 parts by weight (0 ,001 mole parts) of triethylamine. This mixture was dissolved in 50% water. Add liquid sodium hydroxide and stir for 30 minutes while maintaining the pH at 12.5.

19 weight parts were then added to produce the BCB-terminated polycarbonate. Add phosgene to lower pH to 7. This polymer solution was diluted with IN hydrochloric acid and water. Wash and then separate the polymer. According to gel permeation chromatography analysis The weight average molecular weight (Mw) is 31.967, and it is suitable for liquid chromatography analysis. The results showed that BCB-OH was completely reacted. The produced polymer is 58 Compression molded at 5'F (307°C) and completely insoluble in dichloromethane (100 % gel) yielding crosslinked polycarbonate. Glass transition by differential scanning calorimetry The temperature (Tg) was shown to be 160°C. This composition is described below as Experiment 1. A summary and further physical properties are shown in Table 1.

Standard laboratory and test methods were used for polymer analysis and evaluation as shown in Table I. I was able to stay. Mw and Mn are for non-crosslinked preparations, gel permeation chromatography Determined by analysis. The glass transition temperature (Tg) of these materials is Determined by differential scanning calorimetry on heated, crosslinked preparations.

The tensile test was performed on a sample compression molded at 307°C on a 1.6 mm diameter, i.e. 1716 inch. It was carried out regarding the The analysis is based on ASTM D- for Type V sample dimensions. It was done by 638. The tensile modulus is indicated by “Ten Mod” and its value is megapascal (MPa) and kilopounds per square inch (kpsi) is given in parentheses. sample yield and sample The stress required for rupture is expressed as “yield stress” and “rupture stress”, and the value is MP The values in parentheses are given in kpsi. “Sample yield” and “testing” The percentage elongation of the sample at the point of "yield elongation" and "elongation at break" The values shown are the percentage of the stretched sample relative to the original sample. Expressed in centage. Flexural modulus (“F]exMod”) is ASTM D- Tested by 790, given in MPa, in parentheses given in kpsi ing.

Notched Izot impact resistance was measured using ASTM D-256-72A at 307°C. Samples of 3.18 mm (C/a inch) compression molded at

The result (“N, Izod”) is given in joules per meter (J/m). , given in feet, pounds per inch (ft, lb/in) in parentheses. There is.

Percent expansion (% expansion) indicates the resistance of a polymer to solvents and For a 0,254 mm ('/+oo inch) film-like sample moistened with tongue measured. The results shown reflect the percentage increase in polymer surface due to solvent absorption. It is All samples were found to be insoluble in dichloromethane.

Char yield (% char), i.e. 800°C and 5% of the sample lost in air. To determine the percent weight remaining after heating at the decomposition temperature (“Td”) Thermogravimetric analysis (TGA) was used. These results indicate that the polymer according to the present invention is good. This shows that it has a high thermal stability.

The ignition resistance of a polymer composition is determined by the Lirnifying Oxygen Index (LOI). ASTM for a 3.18 mm ('/s inch) sample, UL-94 using D-286:3-87 and D-4804,-88, respectively. A test was conducted.

The coefficient of linear thermal expansion (“CLTE”) is measured using ASTM D-696. It is expressed as a factor of 10-5 per degree temperature (X 10-5/℃), and the value in parentheses is A factor of 10-5 per Fahrenheit temperature (XIO-'/''F) is expressed. Ru.

The scratch hardness test (“hardness”) indicates the abrasion resistance of the sample and meets ASTM D- The test was conducted using 3363. H is the hardest, F, HB, B, 2B, 3B In order, the hardness decreases. Typical carbonate polymers as shown in the table has a hardness of 3B, which is clearly higher than that of standard carbonate polymers. It has excellent hardness.

Table ■ - Composition and property data The polymer was molded at 200°C without crosslinking.

As seen in Table I, a high molar ratio of arylcyclobutene to dihydric phenol This produces carbonate polymers with a low degree of polymerization and low molecular weight. In addition, The physical properties of the molded products tested after crosslinking the polymer composition were surprising. Met. Those skilled in the art will understand that polymers with this degree of crosslinking are generally brittle; One would expect low impact resistance.

In Experiment 10, the method described as Preparation Method A produced 0.13 parts by weight ( 0,0011 mole parts) of 4-hydroxybenzocyclobutene and additional linkages 1.42 parts by weight (0,0095 mole parts) of para-tertiary salts as a stopping compound. Repeated with chilphenol. Prior to activation of benzocyclobutene bond formation The molecular weight (Mw) before branch formation was 29.797. Impressions of polymer Susceptibility to shear between 0.01 and 100 radians per second at 280°C The velocity was determined by melt viscosity measurements. Sensitivity index, Rkyo is 1 la per second It is defined as the ratio of the melt viscosity in radians and 100 radians. Various Among the indexes, the R electric value is an index of the blow moldability of the polymer, and nates are generally better suited for blow molding applications than linear polycarbonate resins. It is believed that Table ■ shows the properties of the branched polycarbonate according to the present invention. The properties of linear bisphenol A polycarbonate resins are compared.

Table ■ - Branched polycarbonate data Experiment number PC control publication 0 0.0037 BCB molar ratio per mole of divalent compound NA O, IBCB mole per mole of other chain-terminating substances Mw 29.400 29.797 n (degree of polymerization) 34 34 Tg (C) 150 154 R umbrella 1.27 1.64 In a further experiment (Experiment 11), we used benzocyclobutene acyl chloride. A functionalized polycarbonate was prepared. Mechanical stirrer in glass reactor, stirring Secondary baffle plate, thermometer, connected to Fisher model 805 pH meter/controller pH electrode, column inlet tube, phosgene inlet tube, 50 weight percent sodium hydroxide A washer with an aqueous solution of thorium and 1 weight percent triethylamine. Attach a gas outlet pipe connected to a phosgene washer. Reactor and melt The medium is thoroughly flushed with nitrogen gas before introducing phosgene. The stirrer is placed over the entire area of the reaction tank. Attach it so that it can be stirred vigorously. Keep the reactor temperature below 30℃.

As mentioned above, 68.5 weight parts (0.3 mole parts) of bisphenol are added to the actor. Tool A, 1.50 weight parts (0,009 mole parts) of benzocyclobutene 4-Carbonyl chloride (BCB-COCl), 360 parts by weight water, 24 Add 0 weight parts of dichloromethane. 48 weight parts (0,6 mo) while stirring Add a 50% aqueous solution of sodium hydroxide (Ruperts), followed by 37 parts by weight. (0,375 mole parts) of phosgene is added at a rate of 1 part by weight/min. water Add sodium oxide to maintain pH 12.5. Next, 515 weight parts dichloromethane and 0.30 parts by weight (1 mole percent) triethyl acetate Add min.

The mixture is stirred for 20 minutes to obtain a BCB-terminated polycarbonate. 9 layers in the mixture Add part of phosgene to lower the pH to 7. The polymer solution was treated with IN hydrogen chloride and Wash with water and then separate the polymer. Gel permeation chromatography analysis An average molecular weight (Mw) of 32,814 was obtained, and the liquid of the remaining components of the reaction mixture was Chromatographic analysis showed complete reaction of BCB-COCl. It was. The results of Experiment 11 are shown in Table ■ below.

Table ■ - Polymer experiment number based on acyl chloride pc control 11 BCB-mo/I/ratio 0 0.03 Mw 30.000 32.000 M　n　12.000　10.900 Mw/Mn 2.50 3.02 n (degree of polymerization) 34 34 7g (C) 150 166 % expansion soluble 225 Submission of translation of written amendment June 1993/Rhoday

Claims (8)

[Claims] 1. prepared from one or more polyvalent compounds; Carbonate having an average degree of polymerization of at least 2 and having a terminal arylcyclobutene moiety. top polymer. 2. The carbonate polymer of claim 1 having an average degree of polymerization of 2 to 100. 3. as claimed in claim 1, having essentially no pendant arylcyclobutene moieties. Gau carbonate polymer. 4. Contains 0.01 to 1 mole of terminal arylcyclobutene per mole of polyhydric compound. A carbonate polymer according to claim 1, which is polymerized to have a carbonate compound. 5. prepared from one or more polyvalent compounds; It has an average degree of polymerization of at least two and a terminal arylcyclobutene moiety; Use of robene-functionalized chain-terminating compounds in carbonate polymer polymerization reactions Therefore, prepared or suitably functionalized arylcyclobutene compounds can be By reacting with reactive moieties located at the ends of polycarbonate molecules A carbonate polymer according to claim 1 prepared. 6. Arylcyclobutene chain termination compounds and their Carbonate polymer according to claim 5, using other chain terminators. 7. 0.01 to 0.5 mole of arylcyclobutene per mole of additional chain terminator 7. Carbonate polymer according to claim 6, using a chain-terminating compound. 8. prepared from one or more polyvalent compounds; Both have an average degree of polymerization of 2, and the arylcyclobutene moieties react with each other to cause crosslinking. or a terminal arylcyclobutene such that it forms a polymeric branch. A carbonate polymer composition comprising a carbonate polymer according to.