FI58148B - KOLLOIDAL BLANDNING FOER ANVAENDNING SAOSOM KRYMPNINGSNEDSAETTANDE TILLSATS TILL MALEIN- OCH / ELLER FUMARSYRAPOLYESTRAR - Google Patents

Description

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Federal Republic of Germany-Pörbundsrepubliken Tyskland (DE) P 20l + Ul68.3 (71) Bayer Aktiengesellschaft, Leverkusen, Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (72) Leonhard Goerden, Oedt / Rheinland, Werner Klöker, Krefeld

Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (7 ^) Oy Kolster Ab (5 ^) Colloidal mixture for use as an anti-shrink additive in maleic and / or fumaric acid polyesters

The invention relates to a viscous or granular colloidal mixture which is used as an anti-shrinking additive in maleic and / or fumaric acid polyesters and which consists of a) from about 10 to about 80% by weight, preferably from about 15 to about 50% by weight. polyethylene or ABS resin which are thermally soluble or swellable with polymeric monomers with maleic or fumaric acid polyesters, but which are for the most part insoluble at room temperature, and b) from about 90 to about 20% by weight, preferably n 85 -n. 50 by weight - of styrene, o (~ methylstyrene or vinyltoluene.

The invention is characterized in that it is prepared by a) heat dissolving the polymer in the monomer or swelling the polymer in heat in the monomer, b) optionally adding a pigment dispersion, then cooling the mixture with possible stirring, and optionally filtering off the excess monomer and optionally comminuting the mixture.

Prior to cooling, pigment dispersions may optionally be added to the mixtures. Due to the mixing, the pigments are easily and very evenly distributed, so that they are also finely and evenly distributed in the cooled viscous or possibly 58148 friable colloidal mixtures.

The colloidal mixtures according to the invention are very valuable additives for mixtures of maleic and / or fumaric acid polyesters and polymerizable monomers, since the shrinkage of the polyester mixtures is greatly reduced and shapes with particularly smooth and glossy surfaces are obtained.

This use of the colloidal mixtures according to the invention is more advantageous with regard to the above-mentioned effects than with the known addition of fine polyethylene powder (cf. e.g. German Offenlegungsschrift 1,192,820) and the addition of polymethyl methacrylate solutions according to Belgian patent TOO 910.

The following examples illustrate the preparation of the colloidal compositions of the invention.

Example 1 - 20 parts by weight of high pressure polyethylene powder (melt index according to ASTM-D 1238-62 T 2 g / 10 minutes, density 0.91-9 g / cm 2) are dissolved at 70-90 ° C with vigorous stirring at 80% by weight. part of styrene. After cooling the mixture, a medium viscous, cloudy mass is obtained.

Example 2 From 100 parts by weight of a medium viscous mass obtained according to Example 1, containing 20 parts by weight of polyethylene and 80 parts by weight of styrene, 33 parts by weight of styrene are removed by vigorous suction to give 67 parts by weight of a friable mixture of 20 parts by weight. parts polyethylene and U7 parts by weight styrene (dry matter content approx. 30%).

Example 3

In a manner similar to Example 1, 15 parts by weight of ABS resin is dissolved in 85 parts by weight of styrene by heating. After cooling, a medium viscous, turbid mass is also obtained.

Example U

30 parts by weight of high-pressure polyethylene granules (Melting index 5 * 9 ~ ~ 7 7 * 1 g / 10 minutes, density 0.917 g / cm) are dissolved in 70 parts by weight of n-methylstyrene by heating the mixture at 70-80 ° C with constant stirring. After cooling with stirring, a cloudy mass of medium to high viscosity is obtained.

Example 5 20 parts by weight of a blended polymer containing 60 parts by weight of styrene and 10 parts by weight of UO by weight of β-methylstyrene (intrinsic viscosity, measured with a solution of 5 g of product per 1000 mothers of dimethylformamide at 20 ° C = 19) are dissolved in 80 part of the styrene by heating to about 70 ° C. After cooling with stirring, a low viscosity, turbid mass is obtained.

3 58148

Example 6

The blend polymer used in Example 5 is dissolved in 30 parts by weight of TO to a weight of vinyl toluene with heating with stirring to 70 ° C. After cooling the mixture, a medium viscous, cloudy mass is obtained.

Example 7

The blend polymer used in Example 5 is dissolved in 80 parts by weight of 20 parts by weight of styrene with heating to 100 ° C with stirring. After cooling, a pasty, cloudy mass is obtained.

Example 8

30 parts by weight of a blended polymer with about 55 parts by weight of ethylene and _ about 1 * 5 parts by weight of vinyl acetate (density 0.92, Mooney viscosity AML

(100 ° C) 20, melt index (ASTM-D 1238-62 T, condition E) 0.5- g / 10 min), is dissolved in 300 parts by weight of trichlorethylene with stirring at 70 ° C. After cooling the mixture, a high viscosity, turbid mass is obtained.

Example 9

The blend polymer of Example 8 is dissolved in 30 parts by weight of 70 parts by weight of vinyl acetate with stirring at about 60 ° C. After cooling the mixture, a high viscosity, turbid mass is obtained.

Example 10 30 parts by weight of a polyvinyl chloride emulsion polymer (K value approx. 70, molecular weight approx. 89000) are dissolved in 70 parts by weight of styrene with stirring at approx. 70 ° C. After cooling, a pasty, cloudy mass is obtained.

Example 11 30 parts by weight of a polymer containing about 78% by weight of # polyvinyl butroacetal, about 1-2 parts by weight of # polyvinyl acetate and about 19-20% by weight of # polyvinyl alcohol (density = 1.1, 10- the viscosity of the weight-# # butanol solution at 20 ° C to about 100-200 cP) is dissolved in 70 parts by weight of styrene with stirring at about 100 ° C.

After cooling the mixture, a high viscosity, clear mass is first obtained, which gradually becomes cloudy.

- Example 12 120 parts by weight of the polyethylene granules used in Example 1 * are dissolved with stirring in 1 * 80 parts by weight of styrene at about 100 ° C. Prior to cooling, a color mill prepared in a rolling mill with the following ingredients is added: 500 parts by weight of titanium dioxide, 20 parts by weight of a solution of 65% by weight of unsaturated polyester, the polyester containing 60 molar maleic anhydride, 1 * molar acidic phthalic acid mol / # propylene glycol-1,2 and has a viscosity of 600 cP, and 1.5 parts by weight of a 1% by weight toluene hydroquinone solution in a 65% by weight polyesterstyrene solution). After this mixture is cooled to li 58148 o ......... ....

to about 30 ° C, a further 2% by weight of finely divided acid is added.

A slightly pasty, cloudy mass is obtained.

The following examples illustrate the use of the colloidal compositions of the invention as an additive in blends of unsaturated polyesters and polymerizable monomers.

In this case, two different polyester blends A and B were used.

Seos A

51 to 26 parts by weight of propylene glycol-1,2 are polycondensed with 56.18 parts by weight of maleic anhydride and 3.80 parts by weight of phthalic anhydride .... . ...... o o unsaturated polyester. The esterification temperature rises from about 100 ° C to about 210 ° C, the esterification time is about 13 hours. The polyester has an acid number of 29, and the viscosity of the 55% by weight styrene solution, measured on a DIN plate, is n.

70 seconds.

65 parts by weight of this polyester are dissolved in 35 parts by weight of styrene. The solution is stabilized by the addition of 0.011% by weight of hydroquinone and has a viscosity of n.

2500 cP.

Seos B

As shown in Example 1, equal amounts of propylene glycol, maleic anhydride and phthalic anhydride are prepared in polyester. The esterification time is 12 hours, the polyester has an acid number of 31 and a viscosity of 65 seconds, measured as described in connection with A.

80 parts by weight of this polyester are mixed with 20 parts by weight of styrene and this mixture is stabilized by adding 0.01 U by weight of hydroquinone. Its viscosity is about 10,000 cP.

Example 13 This example compares the production of a compression piece from the mixture a) according to the invention with the production of a corresponding part from the mixture b) according to the Belgian patent 700 910. The following ingredients are mixed thoroughly: _a) _b) _ - _. 60 parts by weight 60 parts by weight

Seos A

30-Weight-Ethical Polymethyl Methacrylate Styrene Solution - ^ 0 "

The mixture according to Example 1 is 1 + 0 parts by weight

Tert-butyl perbenzoate, 95 # 0.75 "0.75"

Zinc stearate 1+ "U"

Kaolin U5 "^ 5"

Titanium dioxide (rutile) 5 "5"

Black iron oxide

Magnesium oxide 1.5 "1.5" 5 58148 26 parts by weight of glass fiber mat are immersed in 7 * + parts by weight of mixture a) or b). After three days, the dipped mats are pressed with a heated steel press at 11 + 0 ° C and a compression pressure of 100 kp / cm 2 into standard bars (6 interconnected flat bars measuring 120 mm x 15 mm x 10 mm). Then there is a linear shrinkage with mixture a) 0.107% and mixture b) 0.148%.

Example This example compares the gloss of trays pressed from the mixtures a) and b) according to the invention on the one hand and from the mixture c) according to the Belgian patent 700 910 on the other hand.

- Thoroughly mix the following ingredients: a) b) c)

Mixture A 60 parts by weight 60 parts by weight 60 parts by weight 30% by weight polymethyl methacrylate-styrene solution

The mixture according to Example 1 kO "- -

Mixture according to Example 2 - 4θ tf -

Tert-butyl perbenzoate (95- *) 0.75 "0.75" 0.75 "

Zinc stearate ^ "U" U "

Kaolin 1 * 5 "U5" 1 + 5 "

Titanium dioxide (rutile) 5 "5" 5 "

Black iron oxide 0.2 "0.2" 0.2 "

Magnesium oxide 1.5 "1.5" 1> 5 "26 parts by weight of a glass fiber mat are impregnated with Jk parts by weight of mixtures a), b) and c). After three days, trays 28 cm x 37 cm are pressed from them.

o 2

The compression temperature is 11 + 0 C and the compression pressure is 100 kp / cm.

The gloss measurements of the trays yielded: 1. In the Gardner gloss meter 1 + 5 - gloss value 80-82 84–86 70-75 2. With the Glassbox standard 163 gloss value 8 88 5

The trays of the mixtures a) and b) have not only a better gloss but also a better color mixing than the trays of the mixture c) and are therefore more evenly colored.

Example 15 This example shows that the viscosity of polyester-styrene blends increases considerably less with the addition of the colloidal mixture according to the invention than with the addition of a corresponding amount of powdered polyethylene, cf. the following table: «58148

Styrene- Viscosity increase in> ?.

Mixture A PE powder Mixture addition U in 6 days in 8 days i + 00 gl »0 g - 18 21 27 311 g UO g 89 g 50 50 311 g - 129 g pre- - 5 - 9 mark 2 .

3U7 g - 77 g according to Example - 3 7 13 2.

Example 16 In addition, polyester molding compounds to which the mixture according to the invention has been added shrink when pressed less than those to which - a corresponding amount of polyethylene powder has been added, as shown in the following example,

The following ingredients are mixed thoroughly.

a) b) c) _

Mixture B 60 parts by weight 60 parts by weight 60 parts by weight

Styrene 32 "- 32"

Polyethylene powder (as in Example 1) - - 12 "

Eg mixture according to 1 - Uo "-

Tert-butyl perbenzoate, 95 - # 0.75 "0.75" 0.75 "

Zinc stearate k "U" h "

Ca-Mg carbonate j6 "76" 76 "

Mg carbonate 37 "37" 37 "

Fiberglass, 26 mm 76 "76” 76 "

Shrinkage 0.19% 0.025% 0.066%

A lot of shrinkage cavities not at all not at all

Example 17 60 parts by weight of mixture A are mixed with Uo parts by weight of the mixture according to Example 3, a further 0.75 parts by weight of tert-butyl perbenzoate (95%), 1 * part by weight of zinc stearate, 70 parts by weight of kaolin, 1.5 parts by weight of magnesium oxide and 70 parts by weight of glass fibers (length about 26 mm) in the order shown in about 2 minutes in a mixing device. The whole mixture is then stirred for a further 5 minutes. After three days, the mixture is pressed into standard rods as described above. The shrinkage is 0.107