JPH0257817B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to thermoplastic molding compositions consisting of cellulose esters or cellulose mixed esters and aliphatic polyesters or polyethers containing carbonate groups as linking groups in the polymer chain. The molding compositions according to the invention are characterized by their excellent compatibility over a wide mixing range and, as a result, by the transparency they retain even on storage. Furthermore, molding compositions consisting primarily of cellulose esters not only exhibit excellent transparency but also unexpected impact strength, especially at low temperatures, which is necessary for many applications. Therefore, the present invention provides from 1 to 99% by weight based on the ingredients and amounts of
containing at least one cellulose ester or cellulose mixed ester of 99 to 1% by weight of carbonate groups as linking groups in the polymer chain and 2000 to 1% by weight of carbonate groups as linking groups;
Thermoplastic molding compositions consisting of at least one aliphatic polyester or polyether having a molecular weight of 300,000, preferably 4,000 to 200,000, and optionally standard auxiliaries and additives. Among the mixtures according to the invention, from 80 to 97% by weight, preferably from 85 to 98% of the components) and 3
~20% by weight, preferably 5-15% by weight)
Mixtures consisting of are characterized by outstanding impact strength. Other suitable mixtures are 1-50% by weight, preferably 10-35% by weight of components) and 99-50% by weight.
, preferably from 90 to 65% by weight of components), since these mixtures are characterized by their transparency even during long-term storage. The cellulose esters used according to the invention are the known esters of cellulose, such as esters with acetic acid, propionic acid or butyric acid,
Alternatively, it can be a mixed ester of cellulose and acetic acid, propionic acid or butyric acid. Their hydroxyl content should be within the range of 0.3-3% by weight, and their melt viscosity should be at 23℃
(20% in acetone/ethanol 9:1)
It should be within the range of 30-18000mPa.s. Hydroxyl content from 0.4 to 2% by weight and from 500 to
10000mPa.s (23℃, acetone/ethanol 9:1
Cellulose esters of _C1 - _C4 carboxylic acids with a viscosity of 10% to 32% by weight, acetyl group content of 10% to 32% by weight, 15% to 40% by weight are preferably used according to the invention.
Butyryl group content of 40% by weight, hydroxyl group content of 0.5-1% by weight and 5000-10000mPa.s
Particularly preferred are mixed esters of cellulose having a viscosity of (23° C. in acetone/ethanol 9:1). Cellulose esters of this type are known and are described, for example, in Kunstsch Handbook, vol. It is written in They are produced by esterifying cellulose in solution in acetic acid or methylene chloride with acetic anhydride, propionic anhydride or butyric anhydride, mixtures thereof, or mixed carboxylic acid anhydrides. The relative viscosity η relative of the cellulose esters used, measured on a 2% solution in acetone at 25° C., is preferably between 3.5 and 5.0, more preferably between 4.0 and 4.5. The cellulose esters used according to the invention can of course also contain standard additives, such as esters of phthalic acid such as dimethyl phthalate or dibutyl phthalate, ethyl derivatives of ginseng or benzene and toluenesulfonamides. It is also possible to contain fuels, such as triphenyl phosphate or trichloroethyl phosphate, or dyes. The second polymer component of the molding compositions of the invention preferably has the following repeating structural units: [wherein x' is the same or different residue of an aliphatic polyester with a molecular weight of 200 to 6000, preferably 1000 to 2500, and x=x' or 200 to 20000, preferably
are the same or different residues of aliphatic polyethers with a molecular weight of 700 to 10,000, 1 is an integer of 1 to 20, n is 0 or an integer of 1 to 20, and m is an integer of ≧20 is an aliphatic polyester and/or polyether carbonate having an average molecular weight Mn of 2000 to 300000, and the compounds have a molecular weight Mn of 0.5 to 2.5 dl/g, preferably 0.8 to 1.5 in tetrahydrofuran. It has an intrinsic viscosity of dl/g. Preparation of transparent molding compositions in which polyethers in which x is the residue of an aliphatic polyether with a molecular weight of 200 to 3500 and n and l are integers of 10 to 20 are stable on storage. Particularly suitable for Suitable polyhydric alcohols for the polyesters from which the residue x' is derived are, for example, ethylene glycol, 1,2- and 1,3-propylene glycol 1,4- and 2,3-butylene glycol,
1,6-hexanediol, 1,8-octanediol, neopentyl glycol, cyclohexanedimethanol, 1,4-(bis-(hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, di-, tri- -, tetra- and polyethylene glycols, di-, tri-, tetra- and polypropylene glycols and dibutylene glycols, which may optionally be mixed with one another.For polyesters from which the residue x' is derived Suitable polybasic aliphatic carboxylic acids are preferably dibasic aliphatic carboxylic acids,
Examples are carbonic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, hexahydrophthalic acid, glutaric acid or mixtures thereof. Instead of using free carboxylic acids, it is also possible to use their anhydrides or their esters with lower alcohols. Suitable lactones for polyesters from which the residue x' is derived are, for example, γ-butyrolactone, θ
- valerolactone, ε-cabrolactone, 7-hydroxy-hexanoic acid lactone or 8-hydroxyoctanonic acid lactone. Suitable hydroxycarboxylic acids for polyesters from which the residue x' is derived are, for example, β-hydroxypropionic acid, γ-hydroxybutyric acid, θ-hydroxyvaleric acid, ε-hydroxycaproic acid,
-hydroxyhexanoic acid or 2-hydroxymethylbenzoic acid or 4-hydroxychlorohexanecarboxylic acid. As the polyether residue x, the following general formula is preferable: [In the formula, the groups R ¹ are the same or different, and H or
a _C1 - _C4 -alkyl group, preferably H or _CH3 ,
and a is an integer from 2 to 10, preferably from 2 to 4, and b is an integer from 2 to 350, more particularly from 2 to 250. Compounds can be used. Examples of such compounds include poly-(ethylene-oxide)-glycols, poly(1,
2-propylene-oxide)-glycols, poly-(1,3-propylene-oxide)-glycols, poly-(1,2-butylene-oxide)-glycols, poly(tetrahydrofuran)-glycols, corresponding Poly(pentylene oxide)-glycols, poly(hexamethylene-
oxide)-glycols, poly(heptamethylene-oxide)-glycols, poly(octamethylene oxide)-glycols, poly(monomethylene oxide)-glycols and copolymers and lumps of e.g. ethylene oxide and propylene oxide. They are copolymers. The polyesters and polyethers containing carbonate groups in the polymer chain are the hydroxyl-terminated polyesters and polyethers shown below. [wherein Ar is a substituted or terminally substituted _C6 - _C10 -aryl group, suitable substituents are in particular _C1 - _C4
-alkyl group and nitro group or halogen atom] or the following formula: [wherein Y has the same meaning as X and X' in formula (), or represents a polyester or polyether of the repeating structural unit of the formula containing a carbonate group in the polymer chain] It can be produced by reacting with bis-aryl carbonates. The reaction is normally carried out at temperatures in the range 110-200°C using transesterification catalysts such as alkali metal or alkaline earth metal phenolates, alkali or alkaline earth metal alcoholates, tertiary amines such as triethylenediamine, morpholine, etc. , pyrrolidone, pyridine, triethylamine, or metal compounds such as antimony trioxide, zinc chloride, titanium tetrachloride, and titanate tetrabutyl ester, and the catalyst is 20 ppm based on the total weight of the reaction components. ~
Used in an amount of 200ppm. Reactive compositions such as these are known and are described, for example, in DE 273 2 718 or DE 271 2 435 and in DE 271 2 435
2651639. Intrinsic viscosity [η] at 25℃ in tetrahydrofuran
(for the definition of intrinsic viscosity see HG Elias, “Makromolekule”, Fteich & Welf-Verlag, Basle, p. 265). Polymer formulations according to the invention contain cellulose esters or cellulose mixed esters, optionally in the presence of stabilizers, subplasticizers, lubricants, pigments, dyes, solvents or optical brighteners. It can be obtained by blending with carbonate group-containing polyesters or polyethers. The mixture is then homogenized on mixing rolls at temperatures up to 200° C., removed in green sheet form and reduced in size for subsequent processing. Mixing can also be carried out in a kneader and the products according to the invention can be taken off in the form of strands or in other forms. In one particular embodiment of the invention, the components of the mixture are homogenized in a single-screw or multi-screw mixing extruder and then granulated. In this case, it is important that the extruder shaft is designed to ensure sufficient mechanical internal mixing.
Another consequence of the strong plasticizing effect of polyesters containing carbonate groups is that the molding compositions according to the invention can be produced at relatively low temperatures (140-180° C.), in which case almost color-free products can be produced. can be obtained. Molding compositions are of course high temperature (180 to 250
It can also be produced at temperatures (℃). It is also possible to produce end products directly in this way, such as films, strands or injection molded articles. Modified cellulose esters according to the invention can also be prepared by dissolving the components of the mixture in a suitable solvent or solvent mixture and then evaporating. The solvent can also be evaporated by casting the film and concentrating the volatile solvent by evaporating it at normal pressure or vacuum at a temperature in the range 0 to 220°C or by evaporation using a degassing extruder. . Examples of suitable solvents are ketones such as acetone, methyl ethyl ketone, cyclohexanone or diethyl ketone, esters such as methyl acetate, ethyl acetate or butyl ester or methyl formate, ethers such as diethyl ether, ethylene glycol or diethylene glycol. methyl, ethyl, propyl or butyl ethers or tetrahydrofuran, amides such as dimethylformamide or diethylformamide, chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane, dichloroethane or dichloroethylene, or substituted or Substituted aromatic solvents such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, nitrobenzene, anisole,
Phenol or cresol. The molding compositions according to the invention can be processed by any of the methods commonly used for processing plastics, for example by injection molding, extrusion or blow molding. One particular advantage of the molding compositions according to the invention is their complete transparency and excellent miscibility of the components. The molding compositions according to the invention can be used for the production of utility articles, for example as household and industrial injection molded articles, in seals, films or other molded articles, or in optical articles, especially laminated glass. It can be used for Examples Preparation of polyesters and polyethers containing carbonate groups in the polymer chain A) Linear ethylene glycol units with an average molecular weight of 608 (determined by measuring the OH number) The polyether, 334.8 parts by weight of diphenyl carbonate and 0.1 parts by weight of sodium phenolate were stirred for 1 hour at a temperature within the range of 160-190°C. The volatile polycondensation products formed, especially the phenols, were then distilled off under a vacuum of 1.5 torr. The temperature was increased to 190° C. for 4 hours while distillation continued. A tacky-elastic material was obtained, which was measured in tetrahydrofuran (THF) at 25°C.
It had an intrinsic viscosity [η] of 0.238 and a molecular weight (determined by vapor pressure osmosis) of ~5000 g/mol. B) 1000 parts by weight of an average molecular weight of 608 and 184
flocculent polyethylene glycol with OH number,
358 parts by weight diphenyl carbonate, 0.1 parts by weight sodium phenolate and 1.2 parts by weight dilauryl dithiopropionate (Irganox
PS800) was treated in the same way as Example A). A rubbery adhesive-elastic material was obtained with an intrinsic viscosity [η] of 0.642 (measured in tetrahydrofuran (THF) at 25° C.). C) 300 parts by weight of adipic acid and a polyester diol of a 65:35 mixture of n-hexane-1,6-diol/neopentyl glycol (average molecular weight Mn 2000, determined by measuring the OH number),
700 parts by weight of a cotton polyether with an average molecular weight Mn of 608 (determined by measuring the OH number),
286.4 parts by weight of diphenyl carbonate, 0.1 parts by weight of sodium phenolate and 1.2 parts by weight of Irganx PS800 are stirred at 185° C. for 1 hour and then the volatile condensation products, especially the phenols, are removed under a vacuum of 1.5 torr for 5 hours. It was distilled off under stirring and at a temperature of 185°C. The product has an intrinsic viscosity [η] of 2.21 (THF
It was a highly elastic rubber with a high elasticity (measured at 25°C). D) 1000 parts by weight of adipic acid and a polyester diol (average molecular weight Mn 2000) of a 65:35 ratio mixture of n-hexane-1,6-diol/neopentyl glycol, 170 parts by weight of diphenyl carbonate, 0.1 part by weight of sodium phenolate. , and 1.2 parts by weight of Irganox PS800 were treated in the same way as the reaction components in Example C). On completion of the reaction, a hydroxyl-terminated polyester containing carbonate groups was obtained with an average molecular weight Mn of 3600 and an intrinsic viscosity [η] of 0.192. E) 420.4 parts by weight of the reaction product of Example A) and 123.2 parts by weight of the reaction product of Example D) were heated to 140° C. with stirring. A vacuum of 0.1 torr was then applied and the phenol formed was distilled off with stirring and heating to 185°C. 9300 measured in the same way as Example A)
A polyether ester containing carbonate groups was obtained after a reaction time of 4 hours with an average molecular weight of and an intrinsic viscosity [η] of 0.61. F) 1000 parts by weight of adipic acid and a polyester diol of a 65:35 weight ratio mixture of n-hexane-1,6-diol/neopentyl glycol (average molecular weight 2000, determined by measurement of OH number),
115.1 parts by weight of diphenyl carbonate and
0.1 part by weight of sodium phenolate was stirred at 150°C under nitrogen for 1 hour, then vacuum was applied and the temperature was increased to 185°C. Volatile condensation products, especially phenols, were distilled off and the vacuum could be reduced to 0.4 Torr as the reaction progressed. After 5 hours of reaction time, the reaction vessel was flushed with nitrogen. The product has an intrinsic viscosity [η] of 1.07 (measured in THF at 25°C)
It was a pale yellow rubber elastic material with a G) 500 parts by weight of adipic acid and 65:35 of 1,6-hexanediol and neopentyl glycol
Ratio of polyester diol mixture (average molecular weight
Mn20000), 500 parts by weight linear polyether of ethylene glycol units (molecular weight 608), 238.6
Parts by weight of diphenyl carbonate groups, 0.1 parts by weight of sodium phenolate and 1.2 parts by weight of dilaurylthiodibrobionate are placed in a reaction vessel covered with a nitrogen atmosphere and with stirring.
Heat to 180°C, condense for 1 hour at 180°C, and then reduce the volatile products in vacuo to 190°C.
It was distilled off by raising the temperature to 1 hour. The product has an intrinsic viscosity [η] of 0.861 (25
It was a solid wax with a temperature of 1.5°C (measured in THF). H 948.5 parts by weight of a linear polyether of ethylene glycol units (average molecular weight 608), 351 parts by weight of diphenyl carbonate and 0.1 part by weight of sodium phenolate were stirred at 160-190°C for 1 hour. A vacuum of 1.5 Torr was then applied and the formed phenol was distilled off. After 4 hours of distillation, no more volatile condensation products escaped. The reaction vessel was then flushed with nitrogen and 160 g of adipic acid and a polyester diol (average molecular weight 2000) of a 65:35 ratio mixture of 1,6-hexadiol and neopentyl glycol were added to the mixture. Vacuum was applied again and the phenol was distilled off at 190°C for 3 hours. The product has an intrinsic viscosity [η] of 0.54
(measured in THF at 25°C) was a very highly viscous oil. I) 6716 parts by weight of adipic acid and 65 of 1,6-hexanediol and neopentyl glycol:
A 35 weight ratio mixture of polyester diol (average molecular weight Mn 2000), 720 parts by weight of diphenyl carbonate and 0.24 parts by weight of sodium phenolate was heated to 130 °C with stirring in a nitrogen-filled, stirrer-equipped vessel with a distillation bridge. Heated. The internal pressure of the reactor was then reduced to distill off the phenol. After 1 hour a pressure of 1 mbar was reached and the temperature rose. The reaction mixture was then heated in vacuo at 150°C for 1 hour.
Stirred at 175°C for 3.5 hours and then at 180°C for 2 hours. A rubbery plastic was obtained with an intrinsic viscosity [η] of 0.99 dl/g, measured in THF at 25°C. Molding Preparations Examples 1 to 9 The cellulose acetate used to prepare solutions having the compositions shown in Table 1 contained 1.55% by weight of hydroxyl groups and
Viscosity of 4400mPa.s (acetone/ethanol 9:1
It was an ester of cellulose and acetic acid with a content of 20%). Films were prepared from the solution and evaluated for transparency after evaporation of the solvent (+=clear; -=
Opacity).

【table】

[Table] Examples 10 to 16 Two sheets of cellulose acetobutyrel (CAB) containing 37% by weight of butyryl groups, 15% by weight of acetyl groups and 0.8% by weight of hydroxyl groups in a screw extruder at 160°C The mixture was mixed with carbonate group-containing polyester F in the weight ratio shown in the table at a parel temperature of , and then granulated. The granules were then injection molded to produce specimens at a melt temperature of 200°C.

Table: The product of Example 16 was opaque after storage for 20 days at 23°C. The products of Examples 14 and 15 remained clear for 40 days when stored at -20°C. Examples 17-19 Cellulose acetobutyrate (CAB) containing 37% by weight of butyryl groups, 15% by weight of acetyl groups and 0.8% by weight of hydroxyl groups was mixed in solution with a solution of polyester C containing carbonate groups. They were mixed in the weight ratios shown in the table. Films were cast from solutions according to the table and evaluated for clarity. Examples 20-22 contain 49-49.5% by weight propionyl groups and 1.6% by weight hydroxyl groups and
Viscosity of 3000mPa.s (acetone/ethanol 9:1
A solution having the composition shown in the table was prepared using cellulose propionate having a concentration of 20%. Films were cast from the solution and evaluated for permeability after evaporation of the solvent.

[Table] Examples 23-25 42-46% butyric acid, 18-21% acetic acid and 0.7-25%
Cellulose acetobutyrate (CAB) containing 1.7% hydroxyl groups was heated at 160 °C on a roll.
The mixture was mixed with carbonate group-containing polyesters as shown in the table. The green sheet was granulated and the granules were then injection molded to produce specimens at a melt temperature of 220°C. Examples 26 to 28 Cellulose propionate (CP) containing 49 to 49.5% by weight of propionyl groups and 1.6% by weight of hydroxyl groups was rolled at 160°C into a polyester containing carbonate groups as indicated in the table. mixed with. The green sheet was granulated and the granules were then injection molded to produce test specimens at a melt temperature of 230°C.

[Table] In the table, ak is the impact strength according to DIN53453 (unit:
kJ/m ² ), an represents the notch impact strength according to DIN 53453 (in kJ/m ² ), and Vicat
represents the bicut softening temperature (Method B) according to DIN 53460 (F: 49.05N) in [°C]).

Claims (1)

[Scope of Claims] 1 1 to 99% by weight of at least one cellulose ester or cellulose mixed ester,
and thermoplastic molding compositions consisting of 99 to 1% by weight of aliphatic polyesters or polyethers containing carbonate groups as linking groups in the polymer chain and optionally standard auxiliaries and additives. . 2 Repeating structural units whose components are as follows [wherein x' is the same or different residue of a polyester with a molecular weight of 200 to 6000, x = x' or the same or different residue of aliphatic polyethers with a molecular weight of 200 to 2000 and 1 is an integer from 1 to 20, n is 0 or an integer from 1 to 20, and m is an integer ≧20], and the compounds are heated at 25°C in tetrahydrofuran. The thermoplastic molding composition according to claim 1, having an intrinsic viscosity [η] of 0.5 to 2.5 dl/g. 3. The thermoplastic molding composition according to claim 1, comprising 80 to 97% by weight of the component and 3 to 20% by weight of the component. 4. The molding composition according to claim 3, comprising 85 to 95% by weight of the component and 5 to 15% by weight of the component. 5. The molding composition according to claim 1, comprising 1 to 50% by weight of the component and 50 to 99% by weight of the component. 6. The molding composition according to claim 5, comprising 10 to 35% by weight of the component and 90 to 65% by weight of the component. 7. The molding composition according to claim 2, wherein in the general formula, the residue x' has a molecular weight of 1000 to 2500 and the residue x has a molecular weight of 200 to 1000.