JPS6092244A - Benzylidenemalonic acid or vinyl benzylidenemalonic acid polyester - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a compound of the general formula [wherein R represents hydrogen, C1-C4 alkyl or phenyl and E is (), or 8-R represents hydrogen and t is 1] , and X and Y may be the same or different and have a structural unit of hydrogen, hydroxyl, methoxy, phenoxy, (/1 to C, alkyl, phenyl, chlorine or bromine), and from 970 to 9000 Molecular weight M
n (measured by a known method by vapor pressure osmosis method or gel chromatography method), OH number of 5 to 115 and 0
It relates to benzylidene malonic acid or νinylogous benzylidene malonic acid polyesters having a COOH number of ~8.

Suitable polyesters have the formula (II) 9- [wherein R represents methyl or ethyl, R2 represents methyl, ethyl or propyl, and n corresponds to Mn of about 2000-84SO, from 3 to 30 ．．
preferably an integer of 10 to 25.

Dihydroxy compounds suitable for the synthesis of the polyesters according to the invention are aliphatic and/or cycloaliphatic dihydroxy compounds and/or diphenols, preferably alfurs with more than two functional groups as branching agents, preferably aliphatic triols or tetraols. 10-20% by mole relative to the amount of dihydroxy compound
, preferably in an amount of 5 to 15 mol%.

The novel polyester containing the structural unit of formula m can be prepared by first reacting with a malonic acid polyester of formula (III) by Knoevenage I [wherein R, i, X and Y are of the formula (T) with the meanings mentioned for (T)]. In this reaction, for example, ○rganicum, ■EB
Deutscher Verlagder 1uis
sensdraften, Berlin, 7th edition, no.
．． General known instructions for this reaction may be followed, such as those presented in Section 2.4, pages 444-447.

The preparation of malonic acid polyesters, i.e. ethyl malonate/glycol polyesters, from diethyl malonate and ethylene glycol, which can be used as starting materials for this reaction, is described by Carol, L+ers, Aroin, J.
, Av, Che+ll, Soc, -51, -12
! 1161') (1929).

Other starting polyesters of malonic acid are similarly prepared.

Acid catalysts such as those commonly known for esterification and transesterification reactions, such as p-)luenesulfonic acid, are preferably used in the preparation of these polyesters. In order to obtain a colorless product in this reaction and on the other hand to achieve a fast reaction, the catalyst is used in the lowest possible concentration, preferably from 0.65 to 0.02% by weight relative to the total amount of reactants. It is preferable that

Branching involves alcohols with more than two functional groups, preferably aliphatic triols or aliphatic tetraols.
up to 20 mol% relative to the moles of the dihydroxy compound,
Preferably, it can be introduced into the starting malonic acid polyester by allowing it to coexist in an amount of 5 to 15 mol %.

In the Knoevenagel reaction, the reactant ratio between the CH2 groups in the starting malonic acid polyester and the C groups of compound (III) is from 1:1 to 1:1.2. The catalyst used is a typical Nebenagel catalyst, such as piperidine/
Glacial acetic acid or ammonium acetate or n-butylamine/
Glacial acetic acid and examples of suitable solvents are aromatic hydrocarbons such as benzene, toluene or xylene. The use of pressure or vacuum is generally not necessary.

Therefore, the present invention provides approximately 51) 11-5 f'l 00
A malonic acid polyester having an Mn of It also relates to a method for producing a 13-polyester containing a structural unit of formula (I), which is reacted.

A further method for producing polyesters containing structural units of formula (T) is based on formula (Ia) -R is methyl or ethyl] in the presence of an acid or base transesterification catalyst such as tetrabutyl orthotitanate or potassium tert-bunarate and under nitrogen at a temperature of 150 to 190°C. As dihydroxy compound and optionally branching agent, an alcohol having more than two functional groups, preferably an aliphatic triol, in an amount of up to 20 mol %, preferably 5 to 15 mol %, based on the number of moles of dihydroxy compound. Or polycondensation with an aliphatic tetraol.

Therefore, the present invention provides a method in which the diester of formula (Ia) is prepared by converting the diester of formula (Ia) in the presence of an acid or basic transesterification catalyst according to known methods.
up to 20 mol %, preferably 5 to 15 mol %, based on the number of moles of aliphatic and/or cycloaliphatic diols and optionally diols, at temperatures between 15 and 190 °C.
The present invention relates to a method for producing a polyester containing the structural unit of formula (1), which is characterized by reacting an alcohol with more functional groups, preferably an aliphatic triol or an aliphatic tetraol, while distilling off the alcohol produced.

The reaction time for the first production method variation is approximately 5 to 10 hours, and the reaction time for the second reaction variation is approximately the same. Separation and purification of polyester according to the present invention includes:
This is carried out according to known methods, for example by washing with water and precipitation with methanol.

The first mentioned production method is preferred because it yields a product of high molecular weight, which is also characterized by an attractively low iodine color number.

The polyesters according to the invention are suitable for use as Hal stabilizers for thermoplastic resins, such as thermoplastic aromatic polycarbonates, thermoplastic aromatic polyesters and thermoplastic C1-C4 alkyl methacrylates.

Therefore, the present invention uses the polyester of the present invention having the structure 111 of formula (1) as a thermoplastic resin, preferably a thermoplastic aromatic polycarbonate, a thermoplastic aromatic polyester or a thermoplastic polyC,-C,alkyl methacrylate. For the UV stabilization of l'), preferably in an amount of 1-1% by weight, based on the weight of the thermoplastic resin.

The polymeric UV absorbers containing structural units of formula (T) which can be used according to the invention can be incorporated into the thermoplastic resin by known methods, for example by adding the polymeric UV absorber to the thermoplastic resin without diluting the polymeric UV absorber. by adding to the melt or by adding polymeric UV absorbers to solid plastics (granules);
by spinning and extruding the mixture at melt temperature or by
This can be done by preparing plastic combinations (masterbatches) with a high content of V@absorbents and subsequently mixing these concentrates with further plastics.゛Therefore, the present invention provides thermoplastic resins, preferably thermoplastic aromatic polycarbonates, thermoplastic aromatic polyesters or thermoplastic polyC1-C, alkyl methacrylates, according to known methods, without further treatment, to 250-3
At a temperature of 20°C, an amount suitable for UV stabilization, preferably from 0.1 to 1% by weight based on the weight of the thermoplastic resin.
The polymer of the invention Uv containing structural units of formula (I) in an amount of
homogeneously mixed with absorbent or polymeric UV absorber,
According to the same method, at a temperature of 250 to 320° C., the same thermoplastic resin is prepared, characterized in that it undergoes a mixed phase through an intermediate step of 5 to 10% by weight concentrate in fat. Regarding IIV stabilization method.

The invention also provides a UV-stabilized thermoplastic resin comprising a polyester containing structural units of formula (T) according to the invention, preferably in a content of 0.1 to 1% by weight, based on the weight of the thermoplastic resin. , preferably thermoplastic aromatic polycarbonate, thermoplastic aromatic polyester or thermoplastic poly01-C4 alkyl methacrylate.

Polymeric IJV absorbers and their use for UV stabilization of plastics, in particular thermoplastic polycarbonates, are known (see JP 2,231,531 and JP 2,231,532). However, the polymeric tJV absorbents described therein are C--C polymers containing ester side chain groups, and the polyester of Rikiki's invention has ester bonds in the main chain.

The polymeric IJ V absorbers according to Published Patent Nos. 2,231,531 and 2.18-231.532 are sublimation resistant, and the extinction coefficient of the polymer, taking into account the UV-absorbing component, is It has the advantage that it is always comfortably higher than the extinction coefficient of the polymer mixture (Narrowly Published Patent Nos. 2 and 23).
1,531, pages 3 and 4).

Furthermore, it stabilizes, for example, polycarbonate molding materials mixed with TiO2 pigments without any observed decrease in molecular weight and without any decrease in mechanical properties (Narrow Published Patent No. 2,
231.532, page 2).

However, when using these polymeric UV@absorbers, the protective effect against IJV is similar to that of the corresponding commercially available monomeric UV
For example, the following comparative compounds A and B -C112-C'-ζ.

Promotion of outdoor weathering (12fi)
11 g lamp, WOM.

IJ V absorber λ42o (%) λ,2o (%) None 35% 63% Compound (B) (0.5% by weight) 53.5% 72.5
% Compound (A) (rl, 5% by weight) 38°0% 67.
However, this was not the case when using the polymeric UV absorber according to the invention.

Examples of malonic polyesters suitable as starting materials for the production of UV absorbers which can be used according to the invention are diethyl malonate and aliphatic and/or cycloaliphatic diols and/or diphenols, according to methods known from the literature. It is a product obtained by transesterification from

The following are examples of suitable aliphatic diols: ethylene glycol, diethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol , 2,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-7'ropanediol, 1,5-bentanediol, 1,6-hexanediol, 2,5-hexanediol, 2-Methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 1゜12-octadecanediol and 1,4- Cyclo to 21- xane dimetatool.

Examples of cycloaliphatic diols suitable for the preparation of malonic acid polyesters are 1,4-cyclohexanediol or perhydrobisphenol A, while examples of diphenols suitable for the preparation of malonic acid polyesters are 2,2-bis-
(4-hydroxyphenyl)-propane (bisphenol A), 1,1-bis-(4-hydroxyphenyl)-
Cyclohexane, 2,2-bis-(3,5-dichloro-
4-hydroxyphenyl)-furopane, 4,4'-dihydroxybiphenyl and hydroquinone.

Examples of alcohols with more than two functional groups are trimethylolpropane, glycerol or pentaerythritol.

Malonic acid polyesters suitable for the preparation of the UV absorbers according to the invention are of the formula (1) 22- in which R1, R2 and n have the meaning of formula (II).

Very particularly preferred malonic polyesters are R1=R2
= Formula where CH3 and 11 are numbers from 10 to 25 (simple).

Malonic acid polyesters which can be used as starting materials for the production of UV absorbers according to the invention have a molecular weight of about 500 to about 5
It should have an average molecular weight Mn (number average) of 000 (measured by the known vapor pressure osmometry or gel chromatography method), and an OH number of 5 to 20 and an acid number of 2 to 9. be.

Examples of suitable aldehydes or ketones of formula (III) are 4-
Methoxybenzaldehyde, 4-hydroxybenzaldehyde, 4-phenylbenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, acetate,
Benzophenone and cinnamaldehyde, with 4-methoxybenzaldehyde and 4-phenylbenzaldehyde being particularly preferred.

The following are examples of suitable diesters of formula (Ia):
Diethyl 4-methoxybenzylidenemalonate, dimethyl 4-methoxybenzylidenemalonate, diethyl 4-hydroxybenzylidenemalonate, dimethyl 4-hydroxybenzylidenemalonate, diethyl 4-phenylbenzylidenemalonate and dimethyl 4-phenylbenzylidenemalonate.

The aliphatic and cycloaliphatic diols and alcohols with higher functionality than the two already mentioned for the preparation of the starting polyester of malonic acid can be used to prepare the polymer U\7 absorbent of the invention by a second preparation variation. It is also suitable as a reactant for the preparation from diesters of formula (Ia).

2.2-dimethyl-1,3-propanediol, 2-meadow 2-propyl-1,3-propanediol;
2-diethyl-1,3-propanediol is a polymer UV
A dihydroxy compound suitable for the preparation of absorbents or starting polyesters of malonic acid, 2,2-dimethyl-
1,3-propanediol is a particularly preferred dihydroxy compound.

The benzylidene malonic acid or vinylic benzylidene malonic acid polyesters containing structural units of formula (I) according to the invention are viscous, resin-like products or brittle, glass-like products, depending on their molecular weight. Brittle, glass-like polyesters with softening points of ~70°C are preferred.

Examples of benzylidene malonic acid or vinylic benzylidene malonic acid polyesters according to the invention are p-methoxybenzylidene malonic acid neopentyl glycol borie7. (Mn approx. 3500), p-methylbenzylidene malonate neopentyl glycol polyester (Mn approx. 350
0), and p-chlorobenzylidene malonate neopentyl glycol polyester.

25- Besides the aromatic polycarbonates, aromatic polyesters and thermoplastic polyC1-C, alkyl methacrylates already mentioned, examples of thermoplastic resins suitable for UV stabilization are thermoplastic transparent plastics, e.g. cellulose. ester, PvC or special types of polystyrene.

Thermoplastic resins which can be preferably stabilized are thermoplastic aromatic polycarbonates which can be obtained by reacting diphenols, especially dihydroxydiarylalkane, with phosgene or diesters of carbonic acid, and likewise with unsubstituted dihydroxydiarylalkane. It is derived from However, those containing an aryl group having a methyl group or a halogen atom in the 0-position and/or the m-position with respect to the hydroxyl group are also suitable. Branched polycarbonates are also suitable. An example of a chain-terminating agent used is monophenol. Examples of branched chains are trisphenol or tetraphenol.

Stabilizable polycarbonates have a relative viscosity of 10,000 to 10, determined by relative viscosity measured in CH2Cl226- at 25°C and a concentration of 0.5 g/100+ ol.
0, (l OC1 preferably 20, OOO~4
It has a weight average molecular weight Mlll of 0,000.

Examples of suitable diphenols are hydroquinoperesolcinol, 4,4'-dihydroxyvinyl, bis-(
hydroxyphenyl)-alkane, e.g. +rC+ ~C8
alkylene bisphenols or C2-C8 alkylidene bisphenols, bis-(hydroxyphenyl)-cycloalkanes, such as C5-C18 cycloalkylene bisphenols or 05-CI5 cycloalkylidene bisphenols, or bis-(hydroxyphenyl) sulfides, ethers, ketones, Sulfoxide or sulfone. Further α.

α'-Bis(hydroxyphenyl)-diisopropylobenzene and corresponding nuclear alkylated or nuclear halogenated compounds. 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 2,2-bis-(4-hydroxy-3,5-dichlorophenyl)-furopane (tetrachlorbisphenol A), 2,2 -bis-(4-
Hydroxy-3,5-dibromphenyl)-propane (
Tetrabromobisphenol A), 2,2-bis-(4
-Hydroxy-3,5-dimethylphenyl)-propane (tetramethylbisphenol A) and 1゜1-bis-
Polycarbonates based on (4-hydroxyphenyl)-cyclohexene (bisphenol 2) and also those based on trinuclear bisphenols, such as .alpha.,al-bis-(4-hydroxyphenyl)-0-diisopropylbenzene, are suitable. Further methods for preparing suitable diphenols and polycarbonates are described, for example, in U.S. Pat. No. 3,028,365.
No. 3,062+781 and No. 3,879.347
It is described in the number.

Thermoplastic resins that may be suitably stabilized include di-7-functional and terephthalic acid and isophthalic dichloride (acetyl chloride ratio 7:3 to 3, preferably 1:1), a chain-terminating agent, and, if appropriate, For example, thermoplastic aromatic polyesters based on branching agents. The above-mentioned compounds for the production of polycarbonates are used as diphenols, chain-terminating agents and branching agents.

Aromatic polyesters include acid chloride, diphenol,
It is prepared by an interfacial polycondensation process from a mixture of a chain-terminating agent and, if appropriate, a branching agent. The relative solution viscosity of the aromatic polyester that can be stabilized by the present invention is 1.18 to 2.0,
Preferably 1.2 to 1°5 (25°C with CH2C12 solution)
and 0.5g7100n+1).

Plastics that can be suitably stabilized include thermoplastic polyC1
-C4 alkyl methacrylates, ie polymers of C1-C4 alkyl methacrylates, preferably methyl, ethyl, propyl or butyl methacrylate, preferably methyl or ethyl methacrylate. These are to be understood as meaning both homopolymers and copolymers of methacrylic acid esters. Additionally, methacrylic acid esters and other ethylenically unsaturated copolymerizable monomers 29
- C1~ which can be stabilized according to the invention by copolymerizing up to 9.5% by weight of said other monomers, based on the total weight of
The C4 alkyl methacrylate polymer may consist of 90.5-10% by weight of alkyl methacrylate units and 9.5-0% by weight of other ethylenically unsaturated monomer units.

Examples of other ethylenically unsaturated copolymerizable monomers are (meth)acrylonitrile, (α-methyl)-styrene, bromustyrene, vinyl acetate, C1-C8 alkyl acrylates, aryl(meth)acrylates, ( meth)acrylic acid, ethylene, propylene, N-vinylpyrrolidone, bisulfone or styrene sulfonic acid (salt)
It is.

Polymethacrylates that can be preferably stabilized according to the invention are substances that are soluble in certain organic solvents and therefore have a linear or branched structure.

Polymethacrylates that can be suitably stabilized according to the invention can be prepared by known polymerization methods, preferably by free radical or thermal polymerization. Suitable polymerization methods are those carried out in emulsions, bulks, suspensions or dispersions, in particular emulsion polymerization, but preferably bulk polymerization or solution polymerization. The molecular weight of the polymethacrylates can be varied within a wide range by known methods, for example by using mercaptans as regulators. Typically, the polymethacrylates that may be suitably stabilized according to the present invention will have a molecular weight (or starch) suitable for processing thermoplastics by injection or extrusion.
index or melt index).

The cellulose ester that can be stabilized according to the present invention can be obtained by converting cellulose into aliphatic monocarboxylic anhydride,
Preferably, it is obtained by esterification with acetic anhydride and acetic acid or acetic anhydride and propionic acid. The hydrolysis carried out in the crude solution is limited to lower hydroxyl contents (from 4 to
25) with a slight excess of water.

Oxidative bleaching of the cellulose esters separated from the solution must be carried out such that no oxidizing agent is detected in the final product. If necessary, post-treatment with a reducing agent should be performed.

The OH number is determined by esterifying the free hydroxyl groups of the cellulose ester with acetic anhydride in pyridine. At this time, excess acetic anhydride is reacted with water and back titrated (Reference, C, J, Ma-hn, L, B, Gen
ung and R.P., Williams, Analyses.
-is of Ce1lurlose Derivat
ives, Industrialancl Engine
eeringChemistry, Volume 14, Issue 12,
935-94 (1 (1942)).

The viscosity of the cellulose ester is 0.3 to 0.5 voids, measured as a 20% solution in acetone. Cellulose esters which can be preferably used are acetobutyrate with an acetic acid content of 17-23% by weight and 45-50% by weight.
or, in the case of acetopropionate, a propionic acid content of 61-69% by weight and a propionic acid content of 2-7% by weight.
It has an acetic acid content of The number of OH is usually 4-25.

This weight average molecular weight MIII is 10, (l OO~
1,000°0C) 0, preferably 100,000-5
00,000.

The types of PVC that can be stabilized in the present invention include emulsified PVC, @
Cloudy PVC and vi<LUKU PX1CR: Yes. Measured in cyclohexanone (23°C, 1% solution)
Cherk value is 50-80.

Particularly transparent types of polystyrene which can be stabilized according to the invention are homopolymers of styrene or copolymers of styrene, preferably containing acrylonitrile and/or butadiene and/or malonic esters, in the presence of a catalyst. For example, by suspension polymerization from monomers or mixtures of monomers they are obtained in 10.000 to 600.000 circles.

(M resistance measured in DMF with C=5 g/l and 20° C.). (References on this subject include Beilsteins Hancl.
buch der Org-aniscl-+en C
hemie(“Be1lstein's Handbo
OK ofOrganic Chemistry”) 4th edition, 3rd supplementary volume, vol. 5, pp. 1163-1169, Spr.
inger Verlagl 964, and H, Ohl
inger, Polystyrol, Part 1, 33- Herstellungsverfahren und
Eigenschaftender Products
e (“Polystyrene, Part 1, P
re-parative processes and
Properties of theProduc
ts”), Springer Verlag 9
55).

Processing of the thermoplastic resin containing the incorporated polymer (Ha? absorbent) of the present invention is carried out by known methods such as extrusion or casting, for example European Published Patent No.
It produces a very wide variety of molded articles, especially sheets and panels, including the double-u+ebbed panels specifically mentioned in No. 4.856. Extrusion can be carried out in a conventional extrusion oven at temperatures between 250 DEG and 320 DEG C., with or without the application of vacuum, depending on the nature of the plastic to be extruded. In this process, evaporation of the U-7 absorbent of the present invention does not substantially occur.

A particularly advantageous use of the polymeric UV absorbers according to the invention is in thermoplastic polycarbonate films from 1 to 15% by weight, preferably 3% by weight, based on the weight of the 734-ilm.
It is to be used at a concentration of ~7% by weight. These films here have a thickness of 10 to 100 μm, preferably 2() to 50 μm, for coating molded articles made from thermoplastic resins, such as the above-mentioned thermoplastic polycarbonates, aromatic polyesters or thermoplastic polymethyl methacrylates.
used in thicknesses of Coatings of this type and methods for their application are known (see e.g. Published Japanese Patent No. 1.694,
No. 274 and No. 2.832,676). Second Patent No. 1, which raises the same in connection with the quality of extruded moldings and equipment for evaporation in the case of vacuum extrusion, among others.
No. 187,902 or Narrow Publication Patent No. 2,310.13
Compared to the use of the monomeric benzylidene malonic ester according to No. 5, particular advantages are offered for the coextrusion of multilayer systems under vacuum.

The present invention therefore provides benzylidene malonic acid or vinylic benzylidene malonic acid polyesters containing structural units of formula (I) according to the invention, based on the weight of the film.
10-100μ■ consisting of thermoplastic aromatic polycarbonate containing 15% by weight, preferably 3-7% by weight;
Preferably it concerns a film with a thickness of 20-50 μm.

The invention also relates to the use of such polycarbonate films for coating molded articles made of thermoplastic resins, in particular by using coextrusion methods.

Examples of molded articles that are particularly suitable for coating are disclosed in European Published Patent No. 0. (Hollow panel or double web panel according to No. 154,856.

Monomeric compounds of the benzylidene malonic ester type, example i
For example, diethyl 4-phenylbenzylidenemalonate has a lower photostabilizing effect than benztriazole-type UV absorbers such as 2-(2-hydroxy-3-tert-butyl-5-5eC-butylphenyl)benztriazole. is publicly known. °The monomeric benzylidene malonic ester is therefore typically used at about 50% higher concentration than the benzotriazole. Polymer IJV according to the invention
The absorbers not only exhibit a better stabilizing effect than the corresponding monomeric light stabilizers, but also present commercially available benztriazoles, such as 2-(2-hydroxy-3-Lert-butyl-5-5eC-butyl). It also shows a better photostabilizing effect than phenyl)-benztriazole (see Example C, 1).

It is also known that monomeric compounds of the pensydylidene malonate type, such as diethyl 4-phenylbenzylidene malonate, reduce to some extent their mechanical properties, such as notched impact strength, in plastics. In particular, the UV absorbers according to the invention exhibit improved notched impact strength at comparable concentrations (see Example C, 2).

Furthermore, the polymeric UV absorbers according to the invention are more stable to extraction by rainwater than monomeric commercial light stabilizers, and in particular to hydroxyphenylbenztriazole.

The thermoplastic resins stabilized according to the present invention may be supplemented with other stabilizers, antioxidants, mold release agents, and flame retardants commonly known in each thermoplastic resin to be modified. Take. Examples of such are phenols, metal deactivators, sterically hindered amines, etc.

The thermoplastic resins stabilized according to the invention are preferably used in areas exposed to high light doses, for example when building greenhouses, for electric lights, for furniture and for the cases of air-free fixtures. be done.

Example a, 1. 2. Production of malonic acid polyester from 2-dimethyl-1,3-propanediol and diethyl himalonate 3,201) g of diethyl malonate and 2,000 g of 2,2-dimethyl-1,3-propanediol (neopentyl glycol) was heated to 14() to 150°C in a stirring pot to distill off ethanol. After half of the calculated amount had distilled off, the mixture was heated to 170-180° C. for 1 hour under reflux. The ethanol was then distilled off again and a water pump vacuum was applied. As a result, highly viscous malonic acid polyester 3,1
89g (93%) was obtained. Mn28(')0 (determined by vapor pressure osmotic pressure), 011 number 24-25, and acid number 2-25
3°B, 1. Production of benzylidene malonic acid polyester from the above malonic acid polyester (A, ]) Neopentyl glycol malonate polyester 903 g
, anisaldehyde 714g, β-alanine 47.1g
A solution of 47.48 of glacial acetic acid and 47.48 of glacial acetic acid in 260 (1 n+l) of toluene was boiled under a water separator for 12 hours. After filtration and evaporation of the solvent, 21 of methanol was added and the mixture
(Stirred under reflux for 1 hour at 1'C.) The phases were separated and the polyester was dried for 4 hours at 150'C under water pump vacuum.
Molecular weight Mn of 500 (determined by gel chromatography)
, an OH number of 11 to 13, an acid number of 1, and a softening point of 56°C.

B, 20 Production of benzylidene malonic acid polyester from monomeric benzylidene malonic ester by polycondensation method p-methoxybenzylidene malonic acid diethyl (B) 55
．． 6g, trimethyl-1,6-hexanediol 32g
A mixture of 0.2 g of potassium tert-butyrate was heated to 160 to 190°C to distill off ethanol. After the calculated amount of ethanol was removed, the mixture was allowed to cool. The orange residue solidified and gave a tough object. The softening point of this body was approximately 55°C.

C11, Production of stabilized polycarbonate moldings Bisphenol A polycarbonate in granular form (ηrel
= 1,310.0.5 g/CH2CL (measured at 100 ml and 25 °C) with 3% by weight of the 4-methoxybenzylideneneopentyl malonate polyester C) from Example (B, 1) by application by so-called spinning. Mixed. The granules were then passed through a twin-screw extruder to 31) ()°C.
A ribbon was obtained which was again cut into granules.

Hollow panels were manufactured from these granules by conventional extrusion methods.

Test of UV stabilizing effect Hollow panels with a thickness of iomm manufactured by the method described above were
, U, V, accelerated outdoor exposure (u+eatt+eri11
g) The sample was placed in a chamber f (Xmax=313r+ll1) and subjected to an exposure test for 3000 hours. For comparison,
10 mm hollow panels made from the same polycarbonate and containing 2-(2-hydroxy-3-tert-butyl-ri-5ee-butylphenyl)-benztriazole produced in the manner described above were tested for the same period of time. . The light transmission coefficient at 450 nm was determined. The test results are shown in Table 1.

Table 1: Q, U, V, artificial outdoor exposure of hollow panels in the device Light transmission at 450 degrees of 10 mm made from polycarbonate and containing: 41- Hollow panels Initial After 1000 hours After 3000 hours a
) 4-Methoxybenzylidene neobentyl polyester 0.3% 81.2% 77.7% 74.
6%b) 2-(2-hydroxy-3-tert-butyl-3-sec-butylphenyl)-beztriazole 0.3% 81.3% 76.7% 7
2.2% C62, production of stabilized polycarbonate moldingsBisphenol A polycarbonate (ηrel
=1.310.0,5 [? /CH2Cl2100rnl
, measured at 25° C.) by the application of so-called spinning, 0.3% by weight, 2% by weight and 5% by weight of the 4-methoxybenzylideneneopentyl malonate polyester from example (B, 1).
% by weight. The granules were then extruded at 300° C. in a twin-screw extrusion mill to obtain ribbons, which were again cut into granules. Small test bars were made from these granules by conventional injection molding techniques. The notched impact strength of this small test bar is DIN53.
．． 453.

The results are shown in Table 2.

Compound (B), ie diethyl 4-methoxybenzylidenemalonate, was also incorporated as control compound; the results are also shown in Table 2.

Table 2: Diethyl 4-methoxybenzylidenemalonate (
B) and Polymer U according to Example (8, 1) Notched impact strength of polycarbonate containing absorbent as additive (IflJ/llll112) - concentration 0.3
2'Uj4% UV absorber (B) 30.1 16 5. OUV absorber (B, 1) 40 21 10.0 Patent applicant Beyer Toyo Akchengesellschaft

Claims (1)

[Claims] 1. General formula [wherein R represents hydrogen, 01-C4 alkyl or phenyl, and t is 0, or R represents hydrogen and L is 1, and X and Y may be the same or different, and hydrogen, hydroxyl, methoxy, 7e7xy, C1~
has a structural unit of C4 alkyl, phenyl, chlorine or bromine, and has a molecular weight M of 970 to 9000.
Benzylidenemalonic acid or vinyl benzylidenemalonic acid polyester having Oi (number of n, 5-115 and C00r-(number of 0 to 8). 2. General formula [wherein, R1 represents methyl or ethyl, R2 represents methyl or propyl, and n is an integer from 3 to 30.] 3. The polyester according to claim 1, wherein n is an integer from 10 to 25. Claim 2-Claim 2: 4. The polyester according to claim 1, particularly as described below. 5. A polyester having an Mn of 500 to 5000 is heated to a temperature of 20 to 150° C. in the presence of a Knobenagel catalyst by a Knobenagel reaction. A method for producing a polyester according to claim 1, wherein the polyester is reacted with an aldehyde or ketone of the general formula [wherein R, t, X and Y have the same meanings as described in claim 1]. 6. The catalyst is piperidine/glacial acetic acid, or ammonium acetate or n-butylamine/glacial acetic acid = 3- The method according to claim 5. 7. The method according to claim 5, wherein the solvent is an aromatic hydrocarbon. The method according to item 5 or 6. 8. A patent in which the malonic acid polyester is a compound of the general formula [wherein R and [≧] both represent methyl, and 11 is a number from 10 to 25] The method according to any one of claims 5 to 7. 9. Claims 5 to 7, wherein the malonic acid polyester is a transesterification product of diethyl malonate and especially any of the diols mentioned below. 10. The method according to any one of claims 5 to 9, wherein the aldehyde of formula (III) is 4-methoxybenzaldehyde or 4-phenylbenzaldehyde. 11. A diester of the general formula [wherein R, i, X and Y are as defined in claim 1, and R3 is methyl or ethyl] is prepared in the presence of an acid or base transesterification catalyst. At a temperature of 150 to 190°C, 0 to 20 based on the number of moles of aliphatic and/or alicyclic diol and diol
2. A method for producing a polyester according to claim 1, wherein the polyester is reacted with an alcohol having a functionality higher than 2 mole % by a known method and the resulting alcohol is distilled off. 5-12, 5 to 15 mol% based on the number of moles of diol, 2
12. The process according to claim 11, wherein the reaction is carried out using an alcohol of higher functionality. 13.2 The alcohol of higher functionality is an aliphatic triol or an aliphatic tetraol. Claim 11
Or the method described in item 12. 14. The method according to any one of claims 11 to 13, wherein the diol is 2,2-methyl-1,3-propanediol. 15. A method for producing a polyester according to claim 1, substantially as described in Examples B, 1 or B, 2. 16. The polyester according to claim 1, produced by the method according to any one of claims 5 and -15. 17. Use of any of the polyesters described in claims 1 to 1 and 16 for stabilizing thermoplastic Ij (fat U). 18. The thermoplastic resin is not further processed. , 26 - A process for UV stabilization of thermoplastics by direct homogeneous mixing with a polyester according to any of claims 1 to 4 and 16 in a tJV stabilizing amount at a temperature of 50 to 320'C. , any of the polyesters of Claims 1 to 4 and 16 may be added to the polyester in the thermoplastic material prior to further mixing the concentrate with the thermoplastic material.
After an intermediate stage of making a 10% by weight concentrate, 250-32
A method for stabilizing the UV of thermoplastic materials by blending them into thermoplastic materials by homogenizing them at a temperature of 0°C. 20, polyester is 0 based on the weight of the thermoplastic material
．． 20. A method according to claim 18 or 19, ultimately present in an amount of 1 to 1% by weight. 21. Method for UV stabilization of thermoplastic materials substantially as described in Examples C.1 and C.2. 2. A tJV stabilized thermoplastic material containing a polyester according to any one of claims 1 to 4 and 16. 7-23, thickness 10- made of thermoplastic aromatic polycarbonate containing 1. to 15% by weight of the polyester according to any one of claims 1 to 4 and 16, based on the weight of the film. 10 rl mel "^ film. 24. Use of the polycarbonate film according to claim 23 for covering molded articles made from thermoplastic material.