JPS62153318A - Improvement of moldability of polycarbonate resin - Google Patents

Abstract

PURPOSE:To obtain the title resin excellent in heat resistance and moldability, by injection-molding a polycarbonate resin containing specified two kinds of structural units. CONSTITUTION:A polycarbonate resin having a viscosity-average MW of 9500-50000 and containing structural units each containing at least one pendant aromatic group, structural units of formula IV and, optionally, structural units of formula V, obtained by reacting a compound (a) of formula I (wherein X' and Y' are each H, a 1-6 C aliphatic hydrocarbon group, aryl or aralkyl, at least either X' or Y' is aryl or aralkyl and Z' and W' are each H or a hydrocarbon group) with phosgene (b), a bisphenol compound (c) of formula II (wherein X, Y, Z and W are each H or a 1-6 C aliphatic hydrocarbon group and at least either X or W is not H) and, optionally, a bisphenol compound (d) of formula III (wherein A and B are X and Z, respectively) at 0-100 deg.C in an inert solvent in the presence of a catalyst and an acid acceptor such as an aqueous alkali solution or pyridine is injection-molded.

Description

Detailed Description of the Invention [Industrial Field of Application] This invention provides a method for improving the moldability of polycarbonate resin comprising a structural unit containing at least one pendant aromatic group as a unit constituting a carbonate)M combination. It is related to.

[Conventional technology]

Conventionally, polycarbonate resins consisting of constitutional units containing at least one pendant aromatic group as units constituting carbonate bonds are polycarbonate resins from co, -bis(lI-hydroxyphenylnopropane (bisphenol A)). It is known that the heat resistance is superior to that of the so-called polycarbonate resin that has been reprinted. However, such polycarbonate resin
Compared to polycarbonate resins made from bisphenol A, they have poor fluidity and have had problems during molding.

For example, in order to shorten the molding cycle in injection molding, when trying to increase the fluidity of the resin by increasing the temperature of the resin, the high heat tends to cause deterioration of the resin. In addition, if the fluidity is poor, residual stress is likely to occur, resulting in problems such as the inability to obtain satisfactory values for the strength and optical properties of the molded product.

[Purpose of the invention]

In view of the above points, the present inventors have developed a polycarbonate resin that is moldable and processable without impairing the heat resistance of the polycarbonate resin, which is composed of a structural unit containing at least one suspended aromatic fortress as one unit forming a carbonate bond. After conducting intensive studies on improvements to the above, it was discovered that the introduction of a portion of a specific carbonate structural unit met the object of the present invention, and the present invention was achieved.

That is, the present invention provides a polycarbonate resin consisting of a structural unit containing a small number (at least one or more) of aromatic groups suspended as a unit constituting a carbonate bond, and the following general formula (IJ
The molding processability of polycarbonate resin is improved by introducing the structural unit shown by

General formula (IJ However, X, Y, Z and W are hydrogen atoms or aliphatic hydrocarbons having 7 to 7 carbon atoms, and at least one of X and W is not a hydrogen atom.

[Structure of the invention] The present invention will be explained in detail below.

The carbonate bond as used in the present invention refers to a -0-C-O- bond such as that obtained by reacting an alcoholic hydroxyl group or a phenolic hydroxyl group with, for example, phosgene.
Further, the unit constituting carbonate bonds refers to a structural unit constituted between such carbonate bonds.

The polycarbonate resin consisting of structural units containing at least seven or more pendant aromatic groups as used in the present invention can provide pendant aromatic groups, for example, by reacting and polymerizing one or more bisphenol compounds represented by the general formula (IIJ) with phosgene. This can be obtained by

General formula C) , at least one of Y' is an aryl group or an aralkyl group.

2' and W' are hydrogen atoms or hydrocarbon groups.

Examples of bisphenol compounds having the structure represented by the general formula (ID) include bis-(terhydroquine phenylnophenylmethane/,/-bis-(q-hydroxyphenyl)-/-phenylethane 1, l- Bis-(4I-hydroquinphenyl J −/−
Phenylpropane bis-(derhydroxyphenyl)diphenylmethane bis-(l-hydroxyphenyl)dibenzylmethane
etc.

In the present invention, a structural unit represented by the following general formula (IJ) is introduced in order to improve the moldability of a polycarbonate resin comprising a structural unit containing at least one pendant aromatic group.

General formula (I) However, X, Y, Z, and W are hydrogen atoms or aliphatic hydrocarbon groups having 10 carbon atoms, and at least one of X and W is not a hydrogen atom.

When introducing the structural unit represented by the general formula (IJ), it is proposed to use one or more bisphenol compounds represented by the general formula CUJ, for example.

(However, X, Y, Z, and W have the same meanings as in the case of general formula (I).) Examples of bisphenol compounds having the structure represented by general formula C■) include bis-(41-hydroxy -3-methylphenyl)methane/,/-bis-(guhydroxy-3-methylphenyl)ethaneco, 2-bis-(guhydroxy-3-methylphenyl)propanco, nybis-c-derhydroxy-3-ethylphenyl]propanco, Examples include 2-bis-(Dahido axy 3-180 prohylphenylnofrobanco, Corbis-(guhydroquine-,7-seabutylphenyl)propanco, 2-bis-(tI-hydroxy-J-tartbutylphenyl)propane, etc. It will be done.

Furthermore, within the scope of the spirit of the present invention, general formula (I
There is no problem even if a structural unit represented by V) is introduced.

General formula (where A and B are a hydrogen atom or an aliphatic hydrocarbon group having a carbon number of 1 to 2).

When introducing the structural unit represented by the general formula (IVJ), it is proposed to use one or more bisphenol compounds represented by the general formula rV, for example.

General formula (VJ However, A and B have the same meaning as the general formula (IVJ).

Examples of bisphenol compounds having the structure represented by the general formula CV) include bis-(tI-hydroxyphenyl"methane, 1,/-
Bis-(lI-hydroxyphenyl)ethane.

ll/-Bis-(t-hydroxyphenyl)propane, ko, Corbis- Hydroxyphenylfubentane, co9.2-bis-(lI-hydroquinphenylno3-
Methylbutane, -1-bis=[q-hydroquinphenylnohexane, -1bis-(q-hydroquinphenyl)-gumethylbentane, and the like.

Here, as a method for producing a polycarbonate having a structural unit containing at least one pendant aromatic group and a structural unit represented by the general formula (IJ), one or more bisphenol compounds represented by the general formula (nJ) are used. When producing a polycarbonate resin, a method is proposed in which one or more bisphenol compounds represented by the general formula CIIr) are copolymerized or separately polymerized and mixed. When producing polycarbonate resin using two or more bisphenol compounds of the general formula (IIJ and general formula C), if the constituent sites represented by the general formula (IV) are also introduced within the range not exceeded, the general formula ( It is proposed to copolymerize at least i bisphenol compounds represented by VJ, or to mix separately polymerized compounds.

Specifically, the method for polymerizing polycarbonate resin is to add an alkaline aqueous solution or pyridine as an acid acceptor to a bisphenol compound in the presence of an inert solvent such as methylene chloride, cordichloromethane, etc., and react while introducing phosgene. . When using an alkaline water bath solution as a reed receptor, the reaction rate can be increased by using a tertiary amine such as trimethylamine or triethylamine or a q-class ammonium compound such as tetrabutylammonium chloride or benzyltributylammonium bromide as a catalyst. Further, if necessary, phenol or a phenol equivalent to p-tert-butylphenol is allowed to coexist as a molecular weight regulator.

The reaction temperature is 0-100°C. The catalyst may be added from the beginning, or may be added after the oligomer is produced to increase the molecular weight.

The method of copolymerization is (a) First, it is simultaneously reacted with phosgene and polymerized.

After reacting to some extent with phosgene, other substances are added and polymerized.

e-y) Separately react with phosgene to create oligomers, and then react and polymerize them.

Any method can be used.

Further, as a method for mixing separately polymerized materials, any method can be used such as a method of mixing the respective powders or granules and then melting and mixing using a kneading roll of an extruder kneader 1 or the like, solution blending, etc.

In the present invention, the moldability of the polycarbonate is improved as the number of structural units represented by the general formula CI) increases among all the carbonate bond positions. In order to maintain the excellent heat resistance resulting from the above-mentioned structural units, the content of the structural units represented by the general formula (I, l) should be 3 to 93% by weight, more preferably 3 to 70% by weight. .

Here, if it is less than 3%, there will be no noticeable improvement effect on molded door workability, and if it is more than 93%, the heat resistance will decrease.

Also, what is the viscosity average molecular weight of the polycarbonate conveniently used in the present invention? , ! 00-j O,000, more preferably //, 000 to das, ooo. In other words? , ! If r is less than 00, the molded piece will be brittle and undesirable in terms of strength, and if it exceeds go or ooo, fluidity will be poor and molding will be extremely difficult.

Dyes, pigments, fillers, and photosensitizers to the extent that they do not impair the properties of the resin when carrying out the present invention.

It can include additives added to plastics, such as antistatic agents, heat stabilizers, etc.

The polycarbonate resin of the present invention can be used in fields requiring high performance as an engineering plastic, such as optical equipment, mechanical parts, electrical parts, automobile parts, various packaging materials, and various containers, by methods such as injection molding, extrusion molding, and press molding. Widely used.

〔Example〕

The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.

Each measurement value in the same example was determined by the following method.

(Ino average molecular tCM) Polymer A using g/l methylene chloride solution.

From ηsp measured at 20°C, the following formula-7 and formula-
This is a value that can be found from 1.

ηsp/a = C] (/+' η8p)
・・・・・・・・・・・・・・・ l) [η
] = KMα・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
... In the -formula C polymer concentration 1/1 [η] Intrinsic viscosity K/o, -tK/,,
1Jx10-' a O,g JM Average molecular weight Coff Glass transition temperature (Tg) It was determined using a differential scanning calorimeter (manufactured by PerkinElmer), and was used as a measure of heat resistance.

(c) Flow value CQ value was determined according to JIBKA719 and was used as a measure of melt fluidity.

] Mechanical properties 8 Precious resin 10Z injection molding machine, cylinder temperature 300
Molding was carried out at ℃, and the obtained test pieces were determined according to the following formulations.

Heat distortion temperature ASTM D 17g Impact resistance value ASTM D Yu! r6 Bending properties ASTM D 790 Tensile properties AEl'rM 1) 43g or less Specific manufacturing methods for polycarbonate and its oligomer used in the present invention are illustrated as examples. Note that all parts indicating the amounts of components of each composition below are parts by weight.

Example 1 Production of polycarbonate oligomer /, /-bis(Hiro-Hydroxyphenyl/-phenylethane 100 parts Sodium hydroxide 10 parts Water
600 parts methylene chloride
J7. Parts of the above mixture were charged into a reactor equipped with a stirrer and stirred at 20 rpm. 57 parts of phosgene was blown into this for 1 hour to perform interfacial polymerization. After the reaction was completed, only the methylene chloride solution containing the polycarbonate oligomer was collected. The analysis results of the obtained oligomer solution in methylene chloride were as follows.

Oligomer concentration 2λ, 3% by weight [Note 1] Terminal chloroformate group concentration O, Dako standard (Note-)
4-phenolic hydroxyl group concentration 0.0-〇 standard (Note 3
) Note /) Measured by evaporation to dryness.

Aniline hydrochloride obtained by reacting with aniline is neutralized and titrated with an aqueous solution of normal sodium hydroxide.

Kinnushi J) Colorimetric determination of color development when titanium tetrachloride is dissolved in vinegar m solution using 5p4nm.

The oligomer solution obtained by the above method is hereinafter abbreviated as oligomer solution-A.

(Note) Production of polycarbonate oligomer Corbis-(II-hydroxy-J-methylphenylnofuropane 100 parts Sodium hydroxide go part Water
trqo part methylene chloride
kJO part p-tert-butylphenol
Part 4 The above mixture was placed in a reactor equipped with a stirrer and stirred at troo rpm. In this, phosgene 7
Interfacial polymerization was carried out by blowing 0 parts into the solution over a period of 2 hours. After the reaction was completed, only the methylene chloride solution containing the polycarbonate oligomer was collected.

The analysis results of the methylene chloride bath depth of the obtained oligomer were as follows.

Oligomer Q degree 4c, o Weight Terminal low formate group concentration 0.36 Normal terminal phenolic hydroxyl group concentration 0. The oligomer solution obtained by the method of /3 normal or higher is hereinafter abbreviated as oligomer solution B.

eυ Production of polycarbonate Oligo-solution-A 1 part Oligomer solution-B 30 parts Methylene chloride
? Part p-tert-butylphenol i, ig
y5 was charged into a reactor equipped with a stirrer and stirred at sso rpm.

Further, a water solution having the following composition was charged and interfacial polymerization was carried out for 3 hours.

Water (36 parts hydroxide) IJ Umco 3% by weight water bath solution 30 parts triethylamine (weight% water bath R/, 11 m) Subsequently, the reaction mixture was separated and the methylene chloride solution containing the polycarbonate resin was mixed with water, a hydrochloric acid water bath solution, After washing with water, the methylene was evaporated and the resin was taken out. The average molecular weight of this resin is /'I,! It was 00.

Also, from the NMR analysis results, the i of the copolymerized co-cobi-C-derhydroxy-3-methylphenyl)propane is /? , / weight t%. Table 1 shows the properties of this polycarbonate resin.

Implementation 4 PJ: 1 Production of polycarbonate Oligomer solution-A 11.0 parts Oligomer solution-
B 100 parts methylene chloride
90 parts p-tert-buty/II phenol l, 3 parts were charged into a reactor equipped with a stirrer, and s
, s' o rpm.

Furthermore, a water bath solution having the following composition was charged and interfacial polymerization was carried out for 3 hours.

water 5
3 parts hydroxide) IJum 2S weight 1 aqueous solution 3
Part triethylamine-weight i% water soluble g s
, The average molecular weight of the resin taken out after washing Vt using the same recipe as in Example s is /J,! ;00.

In addition, NMR analysis results show that copolymerized co-, 2-
The amount of bis-(p-hydroquine-3-methylphenyl)propane was lIo, s Hts.

The physical properties of this polycarbonate are shown in Table 1.

Example 3 [Production of polycarbonate oligomer] Corbis-(l-hydroxy-J-sec butylphenylnoproban Ioo part Sodium hydroxide Jj part Water
700 parts methylene chloride Jg 3 parts The above-mentioned animal was charged into a reactor equipped with a stirrer and stirred at go rpm. This is Hosdef 113
was blown into the solution over a period of 7 hours to effect interfacial polymerization. After the reaction was completed, only the methylene chloride solution containing the polycarbonate oligomer was collected. The analysis results of the obtained methylene chloride solution of the oligomer were as follows.

Oligomer concentration -23,! rX amount % terminal chloroformate group @ degree 0. II The oligomer solution obtained by the method with ON terminal phenolic hydroxyl group concentration of 0.05ON or more is hereinafter referred to as oligomer mm-c.
It is abbreviated as.

Production of polycarbonate oligomer Bis-[l-
Hydroxyphenylnosiphenylmethane 100 parts Sodium diluted in water 50 parts Water
700 parts methylene chloride
Part JjtO The above mixture was charged into a reactor equipped with a stirrer and stirred at g 00 rpm. 7790 parts of phos was blown into this for 7 hours to effect interfacial polymerization. After the reaction, methylene chloride containing polycarbonate oligomer @
Only the liquid was collected.

The analysis results of the obtained methylene chloride solution of the oligomer were as follows.

Oligomer concentration Koda, 2% by weight Terminal chloroformate group concentration 0. The oligomer solution obtained by the method with J t N-terminal phenolic hydroxyl group concentration of 0.07-N or higher is hereinafter abbreviated as oligomer solution-D.

9 Production of polycarbonate Oligomer solution - 0760 parts Oligomer solution - D 100 parts Methylene chloride 110 parts p-tert-butylphenol 1. Ji,m
was charged into a reactor equipped with a stirrer and stirred at sso rpm.

Furthermore, an aqueous solution having the following composition was charged and interfacial polymerization was carried out for S time.

Water: 6 parts Sodium hydroxide, 5 parts It% water, Armpit parts: Triethylamine, 11% Water, mW 1. After washing with the same recipe as /J, the average molecular weight of the resin was 700.

Further, from the results of NMR analysis, the amount of copolymerized U,2-bis-(Hiro-Hydroquine-J-8eC butyl phenylnoproban) was based on the weight of A1.g.

Table 1 shows the properties of this polycarbonate.

Example Tei (INO Production of Polycarbonate Oligobu) 76.6% aqueous solution of bisphenol A sodium salt prepared by dissolving bisphenol A in an aqueous sodium hydroxide solution.
100 parts P-tert-butylphenol O,
3 parts methylene chloride 0 parts phosgene 7 parts The mixture having the above composition was quantitatively supplied to a pipe reactor to perform interfacial polymerization.

The reaction mixture was separated and only the methylene chloride solution containing the polycarbonate oligomer was collected.

The analysis results of the obtained oligomer solution in methylene chloride were as follows.

Oligo concentration: 4'', s*'llt% Terminal chromate group concentration /, J standard Terminal phenolic hydroxyl group concentration: 0.3 normal or more The oligomer solution obtained by the method is hereinafter abbreviated as oligomer solution-E. .

(o) Production of polycarbonate Oligomer solution-A /Otsu S part oligomer solution-B Octopus part oligomer solution-K
53 parts methylene chloride 10
0 parts p-tearly-butylphenol i,
Charge o fA into a reactor with a stirrer! ;! rOrp
The mixture was stirred at m.

Furthermore, an aqueous solution having the following composition was charged and interfacial polymerization was carried out for 3 hours.

water 30
IJ Umco S heavy water bath liquid 3
7 parts Triethylamine co-weight 1.2 parts Example 1
The average molecular weight of the resin taken out after washing using the same formulation as above was /II, -〇〇.

Also, from the NMR analysis results, the amount of copolymerized co-cobis-(gu-hydroxy-3-methylphenyl)jo is /de,rtt%, and the amount of bisphenol A is co-O6.
It was a heavy sound.

The physical properties of this polycarbonate are shown in Table 1.

Comparative Example/Manufacture of polycarbonate Oligomer bath liquid-A 740 parts p-tearly butylphenol 0.5 parts methylene chloride gO parts The above mixture was charged into a reactor equipped with a stirrer and stirred at SSO rpm. Further, add 7 parts of a water bath solution having the following composition, i.e., 7 parts of hydroxide, 1% water bath solution, 1% triethylamine solution,
Interfacial polymerization was carried out for one hour, the reaction mixture was separated, and the methylene chloride solution containing the polycarbonate resin was washed with water, hydrochloric acid (underarm), and then water, and finally the methylene chloride was evaporated and the resin was taken out. The average molecular weight of this resin is i
It was t,'yoo.

The physical properties of this polycarbonate are shown in Table 1.

Comparative Example 2 Production of polycarbonate A polycarbonate was produced in the same manner as in Comparative Example 1 above, except that p-tert-butylphenol was changed to 0.7 parts. The average molecular weight of this resin is /Q, /
It was 00.

The physical properties of this polycarbonate are shown in Table 1.

Comparative Example J Polycarbonate production oligomer solution-f:! 240 copies p-
Tertiary-butylphenol', q i (
Charge 720 parts of S methylene chloride into a reactor with a stirrer! r! Stir at r Orpm.

Furthermore, an aqueous solution having the following composition was charged and interfacial polymerization was carried out for one hour.

water
70 parts sodium hydroxide - 31% violet aqueous solution
It part triethylamine double 2% water bath solution
1.2 parts After washing with the same formulation as in Example 1, the average molecular j of the resin taken out was io and goo.

The physical properties of this polycarbonate are shown in Table 2.

Comparative Example DA Production of polycarbonate Oligomer solution-K/Aσ part p-tert-butylphenol 0.7 part methylene chloride lJO part The above mixture was charged into a reactor equipped with a stirrer, and! ! Stir at r Orpm.

Further, an aqueous solution having the following composition, i.e., was added, interfacial polymerization was carried out for about /,j hours, the reaction mixture was fractionated, and the methylene chloride solution containing the polycarbonate resin was washed with water, hydrochloric acid/water G solution, and then water. , fJ+
Afterwards, methylene chloride was evaporated and the resin was taken out.

The average molecular weight of this resin was 1teoo.

The physical properties of this polycarbonate are shown in Table 1.

〔Effect of the invention〕

As described above, the polycarbonate resin according to the present invention has higher melt flowability when compared at the same molecular weight than a polycarbonate resin consisting only of structural units containing at least one pendant aromatic group, and has excellent moldability. has been improved.

10,000 - Regarding the heat resistance, which is a feature of polycarbonate resins composed of structural units containing at least one such pendant aromatic group, it has a superior value compared to commercially available polycarbonate resins without impairing its heat resistance. showed that.

Therefore, the polycarbonate resin obtained by the present invention has good moldability and excellent heat resistance, so it can be used in a wide range of fields requiring high performance as an engineering plastic.

Claims (1)

[Claims] (1) A polycarbonate resin containing a structural unit containing at least one pendant aromatic group and a structural unit represented by the following general formula (I) as a unit constituting a carbonate bond is injection molded. Method for improving moldability of polycarbonate resin General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼ (However, X, Y, Z and W are hydrogen atoms or carbon atoms with 1 to 1 carbon atoms)
6, and at least one of X and W is not a hydrogen atom. )