JPS5914069B2 - thermoplastic molding composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION It is known to convert high molecular weight thermoplastic polycarbonates based on 35 aromatic dihydroxy compounds into thermoplastic materials with different properties by means of high filler contents.

For example, the modulus and flexural strength of thermoplastic aromatic polycarbonates range from 10% to 4% by weight of the total composition.
Significant improvements can be made by adding 0% glass fiber. A disadvantage of these highly filled polycarbonates is poor processability due to low melt fluidity. The reinforced polycarbonate
Due to its high flexural strength, stiffness and high modulus of elasticity, it is used preferentially in the production of housing components and structural components.

One of the obstacles to more widespread use is the low flowability of these products, which makes production of thin-walled products impossible. Surprisingly here, the weight is 1-7 (
! The addition of small amounts of polyalkylene-isophthalates such as I noticeably changes the flow properties of these glass fiber reinforced polycarbonate melts without significantly changing other properties of these polycarbonates. It was found that it was improved.

The hardness of the polycarbonate remains completely intact. In addition, polyester additives create better adhesion between the glass fibers and the polymer mixture. In contrast, unreinforced polycarbonates of the same molecular weight show only little, if any, improvement in melt flow with the addition of 0.5-10% by weight of polyalkylene-isophthalates. do not have.

Although the addition of even larger amounts of polyalkylene-isophthalates leads to a further linear improvement in the flowability of the molding compound, it at the same time reduces the properties of the polycarbonate, such as resistance to heat strain, impact strength, etc. let

The subject of the invention is thus a thermoplastic, high molecular weight, aromatic polyester based on diphenols.

consisting essentially of 10% to 40% by weight of glass fibers, based on the total mixture, and from 1 to 7(f) by weight, based on the total mixture, of polyalkylene glycol isophthalene, It is a free-flowing thermoplastic molding material. High molecular weight, thermoplastic, aromatic polycarbonates suitable for mixtures in the sense of the invention are prepared from diphenols and phosgene or from bis-chlorocarbonate esters of diphenols according to known methods for phase interfacial polycondensation. It is something to do.

Other suitable high molecular weight, thermoplastic, aromatic polycarbonates are those which can be obtained by the reaction of bisphenol A and diphenyl carbonate according to known transesterification methods. The molecular weight (Mw) of the polycarbonate to be used according to the invention is between 10,000 and 100.
,0001, preferably 20,000 to 40,000. Examples of suitable diphenols include bis(hydroxyphenols) such as hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, eg C,~C8-alkylene- and C2-C8-alkylidene-bisphenols. -alkanes, such as C5-C,5
-cycloalkylene- and bis-(hydroxyphenyl)-cycloalkanes such as C, ~Cl5-cycloalkylidene-bisphenol, bis-(hydroxyphenyl)-sulfide, ether, -ketone, -sulfoxide or -sulfone class, and α, α and screw one (
hydroxyphenyl)-diisopropylbenzene, as well as the corresponding alkylated or halogenated compounds. 2,2-bis-(4-hydroxyphenol(ha)-propane (bisphenol A), 2,2'-bis-
(4-hydroxy-3,5-dichlorophenyl)-propane (tetrachlorobisphenol A), 2,2-bis-(4-hydroxy-3,5-dibromophenyl)-propane (tetrapromobisphenol A), 2,2-bis-(4-hydroxy-3,5-dimethylphenyl)-
Propane (tetramethylbisphenol A), 2,2-
Polycarbonates based on bis-(4-hydroxy-3-methyl-phenyl)-propane and 1,1-bis-(4-hydroxy-phenyl)-cyclohexane (bisphenol Z), as well as e.g. Preference is given to those based on trinuclear pisphenols, such as p-diisopropyrubenzene.

Other bisphenols suitable for the production of polycarbonates are described in U.S. Pat. No. 3,028,365.
No. 2,999,835, No. 3,148,172, 3
, 271,368, 2,970,131, 2,99
No. 1,273, No. 3,271,367, No. 3,280,0
No. 78, No. 3,014,891 and No. 2,999,84
No. 6, as well as German patent application specification P2, O63, O
5O (LeAl3359), P2, O63, O52 (LeAl3425), P2, 2ll, 957 (Le
Al424O) and P2, 2ll, No. 956 (LeA
14249).

Suitable glass fibers in the sense of the present invention include all commercially available grades and types of glass fibers, i.e. chopped, provided that they are finished to be compatible with the polycarbonate by use of appropriate sizes. glass filaments (long glass fibers and short glass fibers)
, roving or stable fiber. The length of the glass filaments, whether or not they are bundled to form fibers, should be between 60 mT1 and 6 mT1 in the case of long glass filaments, while
For short glass filaments, the maximum length is 5m1L (
5,000 Itm) to 0.05 m (50 μm).

The following two types of glass fibers are particularly suitable: 1.6,00
long glass fibers with an average fiber length of 0 Itm, a diameter of 10 μm and a powder content of approximately 1% by weight (50 μm);
and an average fiber length of 2.230 Itm, a diameter of 10 μm and a powder content of 50 (: fl) (<501t
m) crushed short glass fibers.

Materials that can be used are alkali-free aluminum-boromonosilicate glass (6E-glass 1) or alkali-containing "C-glass".

Suitable sizes that can be used are known from the literature.

The aqueous sizing agents known for short glass fibers (see DE 1,201,991) have been found to be particularly suitable for polycarbonate compositions.
Further details on glass fibers and their use in plastics, particularly polycarbonates, can be found in HarrOHagen, Glass Fiber Reinforced Plastics (GlasfaserverstarktO).
KunststOffe), Springer Verlag, Berlin, Götztingen, Heidelberg, 1961 (especially 1
82-252) and U.S. Pat. No. 3,5
No. 77,378 (Ue2l59-Cip).

The reinforced polycarbonate can also contain, as optional additives, pigments such as TiO2, as well as other fillers and other additives, without interfering with the various properties.

Polyalkylene glycol isophthalates in the sense of the present invention include, for example, ethylene glycol, 1,3
-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis-hydroxy-methylcyclohexane and bisphenol A bis-glycol ether. Polyesters, known per se, are based on aliphatic, cycloaliphatic and aralkyl diols, such as, and mixtures of these diols. In polyalkylene isophthalates in the sense of the invention, which are known per se, up to 75 mol % of the isophthalic acid can be replaced by aliphatic, cycloaliphatic and aromatic dicarboxylic acids.

Examples of aliphatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; examples of cycloaliphatic dicarboxylic acids include:
1,4-cyclohexanedicarboxylic acid. Examples of aromatic dicarboxylic acids that may be mentioned are o-phthalic acid,
Terephthalic acid, 1,5- and 1,6-naphthalenedicarboxylic acid, 4,4'-, 4,3'- and 3,3'-
Diphenyl dicarboxylic acid and 4,4'- and 3,
3'-diphenylsulfonedicarboxylic acid. These dicarboxylic acids can optionally have alkyl or halogen substituents. Molecular weight (Mw) of polyalkylene glycol isophthalates in the meaning of the present invention
) is 10,000 to 80,000. These can be obtained, for example, from dicarboxylic acids or their dialkyl esters and the corresponding diols according to methods known per se (for example, U.S. Pat. Nos. 2,647,885, 2,643, 98
No. 9, No. 2,534,028, No. 2,578,660
No. 2,742,494 and No. 2,901,46
(See No. 6). For example, bis-hydroxy-alkyl esters of isophthalic acid can be prepared by using a lower alkyl ester of isophthalic acid, preferably dimethyl ester, as starting material and transesterifying it with an excess of diol in the presence of a suitable catalyst. give.

In this step, the temperature starts from 140°C,
Raise the temperature to 210-220°C. The liberated alcohol is distilled off. Condensation is then carried out at a temperature of 210-280°C, during which the pressure is increased stepwise to 1 mmH.
Excess diol is distilled off, reducing the diol to below 9. The molding compositions according to the invention based on aromatic polycarbonates can be produced according to methods known per se.

That is, the polycarbonate is combined with a filler, a polyalkylene glycol isophthalate, and, optionally, a pigment.
By processing in a single or twin screw extruder with stabilizers and other additives, homogeneous thermoplastics can be provided.

However, the pre-strengthened polycarbonate
It is likewise possible to subsequently homogenize with polyalkylene glycol isophthalate. The subsequent compounding step consists of intensive mixing of the components in an internal mixer followed by ribbon granulation. The mixing time and mixing temperature are selected such that no significant formation of copolyester-carbonate by intermolecular transesterification occurs, i.e., essentially only a physical mixture is formed, within which the polymer is present in a homogeneous distribution. You have to choose as follows.

The mixture is thus generally prepared at a temperature of 250-300°C, preferably 270-290°C.
At such temperatures, the mixing time should not be longer than about 5 minutes. The polycarbonate molding composition according to the invention can be used for all kinds of geometrically stable moldings, such as housing components and structural components, where high elastic modulus, flexural strength and stiffness combined with good toughness are required. It can be used when necessary. The following reference examples, comparative examples and inventive examples are intended to illustrate the subject matter of the present invention in more detail.

Example 1 (Reference Example) Preparation of polycarbonate Approximately 454 parts of 4,4'-dihydroxydiphenyl 2,
2-Propane and 9.5 parts of p-tert-butylphenol are suspended in 1.51 parts of water.

Nitrogen is passed through the reaction mixture for 15 minutes while stirring to remove oxygen from the reaction mixture in a 3-tubular flask with a stirrer and a gas inlet tube. Then 355 parts concentration 4
Add 5% sodium hydroxide solution and 1000 parts of methylene chloride. Cool the mixture to 25°C. While maintaining this temperature by cooling, 237 parts of phosgene are added to 1
Add over 20 minutes. After 15 to 30 minutes or after phosgene absorption has begun, add an additional 75 parts of 4
Add 5% strength sodium hydroxide solution.

1.6 parts of triethylamine are added to the resulting solution and the mixture is stirred for an additional 15 minutes. Obtain a highly viscous solution. The viscosity of the solution is adjusted by adding methylene chloride. Separate the aqueous phase. The organic phase is washed with water until salt and alkali are no longer present. Isolate the polycarbonate from the washed solution and dry. It has a relative viscosity of 1.29-1.30, measured as a 0.5% strength solution in methylene chloride at 25°C. This corresponds to a molecular weight (W) of approximately 31,000. The polycarbonate thus obtained is extruded and granulated. Example 2 (Reference Example) Production of polyethylene glycol isophthalate 97 parts of isophthalic acid dimethyl ester, 71 parts of ethylene glycol, 0.15 parts of anhydrous calcium acetate and 0.4 parts
of antimony trioxide is introduced into a round-bottomed flask equipped with a distillation apparatus, an air condenser and a gas introduction capillary.

Remove air from the apparatus by suction and introduction of nitrogen. 1
Each component is melted by heating to 70°C.

A small flow of nitrogen is passed through the capillary. The methanol formed during the transesterification, which begins immediately, is distilled off. After about 1 hour, the methanol distillation decreases, but the temperature is increased to 200° C. for 2 hours, in the process removing the remaining methanol. Thereafter, excess ethylene glycol is distilled off at 220°C and the temperature is raised to 270°C. At this temperature, the apparatus is gradually depressurized to about 0.3 mm Hg, during which polycondensation to give polyethylene glycol isophthalate takes place, with the exclusion of ethylene glycol. After a further 3 hours the reaction is complete. The polyethylene isophthalate obtained has a concentration of 2%, measured at 25° C. as a 1% strength solution in a solvent mixture consisting of equal parts of phenol and tetrachloroethane.
．． It exhibits a relative viscosity of 0.01, which approximately corresponds to a molecular weight (Mw) of 25,000. Example 3 (Reference Example) Preparation of polybutanediol iso/terephthalate from 1,4-butanediol and 40% isophthalic acid dimethyl ester and 60% terephthalic acid dimethyl ester.

40 parts of isophthalic acid dimethyl ester, 60 parts of terephthalic acid dimethyl ester, 65 parts of butanediol and 0.02 parts of tetraisopropyl-0-titanate were added to a round tube equipped with a distillation apparatus, an air condenser, and a gas introduction capillary. Introduce into bottom flask.

Remove air from the device by suction and backfilling with nitrogen.
Each component is melted by heating to 160°C.

A small flow of nitrogen is passed through the capillary. The methanol formed during the transesterification, which begins immediately, is distilled off. After 1 hour, methanol distillation decreases, so the temperature is increased to 180° C. for 2 hours, followed by a further increase to 200° C. for 1 hour, during which time remaining methanol is removed.

After that, the temperature was raised to 260℃ and the pressure was increased to 0.3m.
Excess butanediol is distilled off while reducing the temperature to uHg. This temperature is maintained for 45 to 60 minutes, during which time polycondensation to give polybutanediol iso/terephthalate takes place with discharge of butanediol. The polybutanediol iso/terephthalate thus formed has a concentration of 2.1%, determined at 25°C as a 1% strength solution in a solvent mixture of equal parts phenol and tetrachloroethane.
It has a relative viscosity of 0.

This corresponds to a molecular weight (Mw) of approximately 28,000. Example 4 (Reference example) 90 mol% isophthalic acid dimethyl ester, 1001
) of polyethylene glycol isophthalate/sebacate from sebacic acid dimethyl ester and ethylene glycol.

87 parts of isophthalic acid dimethyl ester, 9.2 parts of sebacic acid dimethyl ester, 71 parts of ethylene glycol, 0.15 parts of calcium acetate anhydride and 0.4 parts of antimony trioxide were added at a temperature during the condensation of 280 The reaction is carried out as in Example 2, except that the temperature is 260°C instead of 260°C.

The polyethylene isophthalate/sebacate produced is
It has a relative viscosity of 2.30, measured at 25° C. in a solvent mixture consisting of equal parts phenol and tetrachloroethane. This corresponds to a molecular weight (Mw) of approximately 32,000. Examples 5 to 14 (Comparative Examples and Inventive Examples) Polycarbonate used: A. Polycarbonate from Example 1.

B. Reinforced polycarbonate consisting of 70 (Ft) by weight polycarbonate from Example 1 and 30% by weight short glass fibers with a maximum length of about 11 Lm.

C. 80% by weight, prepared according to example 1, Ivw=3
3,000 bisphenol A-based polycarbonate and 20% by weight of long glass fibers, approximately 6 mm long, reinforced polycarbonate. D. Polyethylene glycol isophthalate from Example 2.

E. Polyethylene diol iso/terephthalate from Example 3.

F. Polyethylene glycol isophthalate/sebacate from Example 4.

G. Poly-1,4-bis-hydroxymethyl-cyclohexane-isophthalate, Mw-39,000, prepared as in Example 2.

The table below shows the mixture and its melt index (300℃
, at piston pressure 1.2 kp, DIN 53,73
5).

The mixture is obtained by mixing the components in a twin-screw extruder. Example 15 (Comparative Example) A mixture was prepared from 95 parts of polycarbonate B (glass fiber-containing polycarbonate) and 5 parts of polytetramethylene terephthalate in the same manner as in Examples 5 to 14, and its physical properties were measured.

5) The results were as follows. Rockwell hardness M Elastic modulus [Mpa] Melt index [g/10 minutes] 3.

Claims (1)

[Scope of Claims] 1 (a) An aromatic polycarbonate derived from diphenol, (b) 1 by weight based on the sum of components a, b and c.
0-40% glass fibers, c 1-7% by weight based on the sum of components a, b and c, 25-1 of dicarboxylic acid groups
Polyalkylene glycol dicarboxylate with 00 mole % isophthalic acid groups and 75-0 mole % other aromatic dicarboxylic acid groups, and optionally pigments, fillers, stabilizers and other additives, A thermoplastic molding composition comprising: 2 The polyalkylene glycol dicarboxylate is
ethylene glycol, 1,3-propanediol, 2,
Derived from 2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis-hydroxymethyl-cyclohexane or bisphenol A bis-glycol ether, or mixtures thereof. The composition according to claim 1, which is an isophthalate. 3. The composition according to claim 1 or 2, wherein the polyalkylene glycol dicarboxylate has a weight average molecular weight of 10,000 to 80,000. 4 Polycarbonate is 10,000 to 100,000
A composition according to claims 1 to 3 having a weight average molecular weight of 0. 5 Polycarbonate is 20,000 to 40,000
The composition according to claims 1 to 3, having a weight average molecular weight of . 6. A composition according to claims 1 to 5, wherein the glass fibers have a filament length of 60 mm to 6 mm or a maximum filament length of 5 mm to 0.05 mm. 7 Glass fiber has an average fiber length of approximately 6,000 μm, approximately 1
7. A composition according to claims 1 to 6 having an average diameter of 0 μm and a powder content of about 1% by weight. 8 Glass fiber has an average fiber length of approximately 230 μm, 10 μm
7. A composition according to claims 1 to 6 having a powder content of about 5% by average diameter and weight.