阅读说明：本技术 制备聚碳酸酯模塑料的方法 (Method for producing polycarbonate moulding materials ) 是由 A·赛德尔 T·布勃曼 于 2020-04-08 设计创作，主要内容包括：本发明涉及制备热塑性模塑料的方法,所述热塑性模塑料包含A)至少一种芳族聚碳酸酯和B)另一聚合物,其在化学上不同于聚合物A并且其包含选自下述的至少一种官能团：酯基、环氧基、羟基、羧基和羧酸酐基团,所述方法包括步骤a)在200℃至350℃的温度下,在组分C的催化剂存在下,熔融并混合组分A和B,和b)通过冷却组合物使该组合物固化,其中组分A具有至少3000g/mol的平均分子量Mw,其特征在于,在方法步骤a)中,至少一部分组分A与组分B反应生成共聚物并且其中催化剂C是一种特别的鏻盐,以及涉及通过根据本发明的方法制备的热塑性模塑料和包含该模塑料的成型体。(The invention relates to a process for preparing a thermoplastic molding material comprising A) at least one aromatic polycarbonate and B) a further polymer which is chemically different from polymer A and which comprises at least one functional group selected from the group consisting of: ester groups, epoxy groups, hydroxyl groups, carboxyl groups and carboxylic anhydride groups, said method comprising the steps of a) melting and mixing components A and B at a temperature of from 200 ℃ to 350 ℃ in the presence of a catalyst of component C, and B) solidifying the composition by cooling the composition, wherein component A has an average molecular weight Mw of at least 3000g/mol, characterized in that, in method step a), at least a portion of component A reacts with component B to form a copolymer and wherein catalyst C is a particular phosphonium salt, and to thermoplastic molding compounds prepared by the method according to the invention and to molded bodies comprising the molding compounds.)

1. A process for preparing a thermoplastic molding composition comprising

A) At least one aromatic polycarbonate and

B) another polymer which is chemically different from polymer a and which comprises at least one functional group selected from: ester group, epoxy group, hydroxyl group, carboxyl group and carboxylic anhydride group,

the method comprises the steps of

a) Melting and mixing components A and B in the presence of a catalyst of component C at a temperature of from 200 ℃ to 350 ℃, and

b) the composition is allowed to solidify by cooling the composition,

wherein component A has an average molecular weight Mw of at least 3000g/mol, measured by gel permeation chromatography at room temperature in methylene chloride using a polycarbonate based on bisphenol A as standard,

it is characterized in that the preparation method is characterized in that,

in process step a), at least a portion of component A is reacted with component B to give the copolymer

And wherein catalyst C is a phosphonium salt of formula (4)

Wherein

R₁And R₂Each independently of the other represents C₁-C₁₀An alkyl group, a carboxyl group,

R₃and R₄Each independently of the other represents C₁-C₁₀-alkyl or C₆-C₁₂-an aryl group,

A^n- represents an anion of a carboxylic acid and

n represents 1, 2 or 3.

2. The method of claim 1, wherein component B is a polymer selected from the group consisting of: vinyl (co) polymers comprising structural units derived from alkyl esters of acrylic acid, vinyl (co) polymers comprising structural units derived from alkyl esters of alkyl-substituted derivatives of acrylic acid, vinyl (co) polymers comprising epoxy groups, and polyolefins comprising epoxy groups.

3. The process according to any one of the preceding claims, characterized in that the mixture of components A and B has a residual moisture content of 0.01 to 0.50% by weight, based on the sum of A and B.

4. A process according to any one of the preceding claims, characterised in that component B is polymethyl methacrylate.

5. The process according to any one of claims 1 to 3, characterized in that component B is a polymer selected from: vinyl (co) polymers containing epoxy groups and polyolefins containing epoxy groups.

6. The process according to any of the preceding claims, characterized in that component A is an aromatic polycarbonate based on bisphenol A.

7. The process according to any of the preceding claims, characterized in that in step a) polymer additives and/or other polymer blend partners than components A and B are additionally added as component D.

8. The method according to any of the preceding claims, characterized in that in step a) use is made of

0.5 to 99% by weight of component A,

0.5 to 99% by weight of component B,

0.01 to 0.5% by weight of component C and

0.1 to 50% by weight of component D.

9. The process according to any of the preceding claims, characterized in that process step a) is carried out in a continuous twin-screw extruder with a residence time of 15 seconds to 1 minute.

10. The process according to any of the preceding claims 1 to 3 and 5 to 9, characterized in that polymer B is an epoxy group containing vinyl (co) polymer or an epoxy group containing polyolefin and in process step a) at least 5 mol% of the epoxy groups in polymer B are converted.

11. According to the preceding claimThe process of any of the above, wherein R is in the presence of catalyst C₁And/or R₂Represents n-butyl.

12. The process according to any of the preceding claims, characterized in that in catalyst C, A is^n-Represents an acetate ion or a malonate ion.

13. The process according to any one of the preceding claims, characterized in that catalyst C is tetra-n-butylphosphonium acetate in the form of an acetic acid complex.

14. Thermoplastic molding composition prepared by the process according to any one of the preceding claims 1 to 13.

15. Shaped bodies comprising the thermoplastic molding materials as claimed in claim 14.

Drawings

FIG. 1 shows a schematic view of a

FTIR Spectrum (E represents absorbance, v represents wavenumber)

1: component A1

2: component B1

3: acetone-insoluble portion of molding compound V1

4: acetone soluble portion of molding compound V1

5: acetone-insoluble portion of the molding material 4

6: portion of the molding compound 4 dissolved in acetone

FIG. 2

FTIR Spectrum (E represents absorbance, v represents wavenumber)

1: acetone-insoluble portion of molding compound 5

2: acetone-insoluble portion of the molding material 4

FIG. 3

TEM micrograph of granule microslice of molding compound V9

FIG. 4

TEM photographs of microslices of the pellet particles of molding compound 10.

Table 1:PC/PMMA molding compound and performance thereof

Examples	V1	V2	V3	4	5	V6	7	V8
									Composition of	Parts by weight	Parts by weight	Parts by weight	Parts by weight	Parts by weight	Parts by weight	Parts by weight	Parts by weight
A1	50	50	50	50	50	50	50	50
									B1	50	50	50	50	50	50	50	50
C1		0.05
									C2			0.05
C3				0.05	0.05
									C4						0.05
C5							0.05
									C6								0.05
Water content A + B [ wt.% based on A + B ]]	0.105	0.105	0.105	0.105	0.060	0.105	0.105	0.105
									Performance of
Modulus of elasticity [ MPa]	2748	2875	2799	2838	2809	2741	2831	2779
									Yellow number	39.7	8.2	48.4	1.8	4.7	46.0	2.1	38.9
Haze degree	99.4	11.4	98.7	0.5	7.9	98.4	2.3	99.3

The data in table 1 show that lower yellowness and higher transparency (lower haze) are obtained with catalysts C3 and C5 according to the invention than with catalysts C1 and C2 described in the prior art or with catalysts similar in structure to the catalysts according to the invention, but not with catalysts C4 and C6 according to the invention. Transparency was not achieved without the catalyst (comparative example V1). The use of the catalysts according to the invention also achieves a higher modulus of elasticity than without the use of catalysts, so that it is also possible to consider that a higher surface hardness and thus scratch resistance is obtained.

FTIR studies in FIGS. 1 and 2 show that PC-PMMA copolymer is formed by reaction of component A1 with component B1 in the reactive compounding of the molding compounds 4 and 5 according to the invention, wherein FIG. 2 furthermore shows that molding compound 4 prepared with the preferably higher water content in the mixture of components A1 and B1 forms a greater amount of said PC-PMMA copolymer.

A comparison of the properties of the moulding compositions 4 and 5 according to the invention from Table 1 shows that it is advantageous in respect of optimizing the transparency, the yellowness index and the modulus of elasticity when the polymer components A and B contain at least a small amount of moisture when using the catalysts according to the invention.

Table 2:PC/styrene-propyleneNitrile-glycidyl methacrylate compositions

Examples	V9	10
			Composition of	Parts by weight	Parts by weight
A2	80	80
			B2	20	20
C3		0.05
			Water content A + B [ wt.% based on A + B ]]	0.044	0.044
Performance of
			Epoxide content [ weight ]%]	0.46	0.39
Epoxide conversion (calculated) [% ]]	2	17

The data in table 2 show that in the process according to the invention in the presence of the catalyst according to the invention, a 15% conversion of epoxide can be achieved in the twin-screw extruder with a residence time of about 60 seconds, without this conversion occurring in the process according to the prior art without such a catalyst. Comparison of FIGS. 3 and 4 furthermore shows that by this conversion of the epoxide, a significantly finer phase dispersion of the styrene-acrylonitrile-glycidyl methacrylate terpolymer of component B in the polycarbonate of component A can be obtained.

TABLE 3 PMMA/PC Molding materials and their Properties

The examples in Table 3 show that the PMMA/PC molding composition 14 according to the invention, prepared with the catalyst according to the invention, has better transparency (lower haze), less intrinsic color (lower yellowness index) and higher modulus of elasticity.

Examples

Compositions and components for use therein

Component A1

Makrolon^™ M2408 (Covestro Deutschland AG, Leverkusen)

Aromatic polycarbonates based on bisphenol A

Component A2

Makrolon^™ M2606 (Covestro Deutschland AG, Leverkusen)

Aromatic polycarbonates based on bisphenol A

Component B1

Plexiglas^™ 8H (Evonik Performance Materials GmbH, Darmstadt)

Polymethyl methacrylate

Component B2

Fine-Blend^™SAG-008 (Fine-blend compatilizer Jiangsu Co., LTD, Shanghai, China)

Styrene-acrylonitrile-glycidyl methacrylate random terpolymers. The epoxy content determined in accordance with DIN EN 1877-1 (2000 edition) is 2.35% by weight.

Component C1

Tin chloride dihydrate is more than or equal to 98% (Sigma-Aldrich)

Component C2

Zinc acetate 99.99% (Sigma-Aldrich)

Component C3

Tetrabutylphosphonium acetate-acetic acid complex (Sachem Inc., Austin, USA)

Component C4

Tetrabutylammonium acetate acetic acid complex

Sachem N-416（Sachem Inc.，Austin，USA）

Component C5

Malonic acid tetrabutyl phosphonium more than or equal to 92% (Sigma-Aldrich)

Component C6

Tetrabutylphosphonium p-toluenesulfonate 95% or more (Sigma-Aldrich)

Preparation of thermoplastic moulding materials and moulded bodies

PC/PMMA moulding compounds according to Table 1, V1, V2, V3, 4, 5, V6, 7 and V8 and PMMA/PC moulding compounds according to Table 3, V11 to V13 and 14, were produced on a ZSK26 MC18 twin-screw extruder from Coperion GmbH (Stuttgart, Germany) with a melt temperature of approximately 260 ℃ at the nozzle outlet. An underpressure of 100 mbar (absolute) was applied. The residence time of the melt mixture in the extruder was about 30 seconds.

Moulding compositions V9 and 10 from polycarbonate and styrene-acrylonitrile-glycidyl methacrylate terpolymer according to Table 2 were prepared on a Process 11 twin-screw extruder from Thermo Fisher Scientific Inc. (Calslee Lue, Germany) at a melt temperature of about 260 ℃ at the nozzle outlet. No negative pressure is applied here. The residence time of the melt mixture in the extruder was about 60 seconds.

The molded bodies used for the tests were produced in an injection molding machine model Arburg 270E at a material temperature of 260 ℃ and a mold temperature of 80 ℃.

Determination of the residual moisture content of A and B

The residual moisture content of a and B (also referred to synonymously in the present application as water content) based on a + B is determined by karl fischer titration according to DIN 51777 (2014 version) for the optionally predried components a and B and is determined from the residual moisture values of the components a and B thus determined by the following calculation:

water content of A and B (based on A + B)

= (mass ratio of residual moisture content x A in a + mass ratio of residual moisture content x B in B)/(mass ratio of a + mass ratio of B)

Determination of the conversion of the epoxy functionality

The conversion of the epoxy functionality in polymer B2 on reactive compounding with component A2 was determined by titrimetrically determining the epoxide content in component B2 and in thermoplastic molding compounds prepared therefrom by reactive compounding with component A2 in the presence or absence of the catalyst according to DIN EN 1877-1 (2000 edition). For titration, the sample was dissolved in a mixture of dichloromethane and acetic acid at room temperature with a mixing ratio of 40 ml to 25 ml.

Testing of the Molding Compounds

The modulus of elasticity was determined at room temperature according to ISO 527 (1996 edition).

The yellow and haze values were determined on colour sample plaques having the dimensions 60 mm x 40 mm x 2 mm according to DIN 6174 (2007 edition) and ASTM D1003 (2013 edition).

Detection of copolymer formation in reactive kneading of PC and PMMA

5g of pellets of the thermoplastic PC/PMMA moulding compound to be investigated in each case, prepared in the mixing process, were extracted in 100ml of acetone in a round-bottomed flask with stirring at room temperature (approx. 25 ℃) for 24 hours. The acetone-insoluble fraction of the PC/PMMA molding compound is then separated from the acetone and the extracted acetone-soluble fraction of the PC/PMMA molding compound contained therein by means of filtration. The filtration residue (acetone-insoluble part of the moulding compound) was washed once with acetone in the filter funnel. The insoluble fraction of the PC/PMMA moulding composition was then dried in a circulating air oven at 60 ℃. To recover the acetone-soluble fraction of the PC/PMMA molding compound, the acetone was distilled off from the filtrate by means of a rotary evaporator.

The acetone-soluble and insoluble fraction of the PC/PMMA moulding material thus obtained was then measured by means of FTIR infrared spectroscopy using an FT-IR spectrometer Nicolet Nexus 470 with ATR (attenuated total reflectance) measurement technique of the ThermoFisher Scientific (Calluuer, Germany) in the range from 600 to 4000 cm-1 with a resolution of 1 cm^-1. The CO double bond oscillation is used here for analytical detection and differentiation of polycarbonate from PMMA. For polycarbonatesAt about 1775 cm^-1Is observed in the wavenumber range of (A), and for PMMA, at about 1725 cm^-1Such selective oscillation is observed in the wavenumber range of (a).

Study of Polymer compatibility by Transmission Electron microscopy

The polymer compatibility of components A and B in moulding compositions from polycarbonate and styrene-acrylonitrile-glycidyl methacrylate was investigated with the aid of Transmission Electron Microscopy (TEM). For this purpose, ultrathin sections were produced from the granulate particles of the molding compounds produced in the compounding process described using an EM UC7 microtome from Leica Microsystems GmbH (Wetzlar, Germany). Ultrathin sections were made with a diamond knife and collected in a dimethylsulfoxide/water mixture at-30 ℃. For TEM studies, ultrathin sections were placed on carbon-coated copper grids and incubated with ruthenium tetroxide (RuO)₄) And (6) carrying out comparison. RuO₄The comparison was carried out by an in situ reaction in which 1 ml of sodium hypochlorite solution was added to 13 mg of ruthenium (III) chloride (RuCl)₃) In (1). Thereby forming RuO₄Steam, grid with ultrathin sections was stored for 15 minutes therein. The TEM photographs were carried out in a bright field at an accelerating voltage of 200 kV using an LEO 922A EFTEM transmission electron microscope from Carl Zeiss Microcopy GmbH (Jena, Germany).