DE1269798B - Additive to ester plasticizers - Google Patents

Description

GERMAN WfW PATENT OFFICE EDITORIAL

German class: 39 b -22/01

Number: 1269798

File number: P12 69 798.2-43

J 269 798 Filing date: February 7, 1956

Opening day: June 6, 1968

The invention relates to the use of epoxidized polymers that are 1 to 9.5 percent by weight Contain epoxy oxygen and those made of liquid polybutadiene or a liquid copolymer from at least 60 parts by weight of butadiene and up to 40 parts by weight of styrene have been obtained as Additive to ester plasticizers for solid polymeric organic plastic compounds. According to a preferred Embodiment of the invention is a mixture of 2.5 to 7.5 percent by weight of the epoxidized Polymers and 92.5 to 97.5 weight percent diisooctyl phthalate in an amount of 5 to 100 parts by weight applied per IOO parts by weight of a vinyl polymer. One used according to the invention Epoxidized polymer advantageously contains 2.11 percent by weight of epoxy oxygen and is through Copolymerization of 80 percent by weight butadiene and 20 percent by weight styrene in the presence of Sodium to form an oily olefin polymer having a molecular weight of 10,000 and an ao Viscosity of 1.5 poise with a 100% non-volatile content and subsequent Epoxidation has been obtained.

The advantageous use of these epoxidized polymers as an additive to ester plasticizers to which yet to be discussed, is particularly surprising insofar as it is in accordance with proposals that have not been pre-published such compounds have already been made without affecting their beneficial effects would have been recognized as an additive to ester plasticizers.

The epoxidation takes place at temperatures between 0 and 95 ° C., preferably between 20 and 50 ° C. The reaction time depends on factors such as the temperature and the desired degree of epoxidation. The usual reaction time is between 1 and 60 hours, preferably between 6 and 30 hours. The molar ratio of the C ₄ units contained in the liquid polymer to the peracid can be 1: 1 to 4: 1, preferably 2: 1 to 3: 1. The product obtained contains 1 to 9.5 percent by weight epoxy.

The nature of the epoxidized product depends largely on the degree to which the epoxidation occurs is carried out, the reaction time and temperature and the nature of the starting product. The reaction can be carried out so that a solid product is obtained which is in hydrocarbons is insoluble. However, the epoxidation can also be carried out in such a way that a viscous or semi-solid product is formed which is in hydrocarbons is soluble.

The ever more extensive use of an additive to ester plasticizers

Applicant:

Esso Research and Engineering Company,
Elizabeth, NJ (V. St. A.)

Representative:

Dr. W. Beil, lawyer,

6230 Frankfurt-Höchst, Adelonstr. 58

Claimed priority:

V. St. v. America 8 February 1955 (486 972)

of plastics such as vinyl chloride polymers or copolymers, polyvinyl acetate, cellulose esters, Acrylic ester and methacrylic ester resins and rubbers such as the emulsion copolymers of butadiene with styrene or acrylonitrile or the copolymers of isobutylene with small amounts of a diolefin, such as isoprene, created a great demand for suitable plasticizers. So are alkyl esters, like the esters of open-chain dibasic acids, e.g. B. Esters of sebacic acid, adipic acid, and alkyl phthalates, such as di-2-ethylhexyl phthalate, di-isooctyl phthalate, di-n-octyl phthalate, and higher oxophthalates and tri-2-ethylhexyl phosphate is used as a plasticizer for the high molecular weight materials mentioned.

For some areas of application, however, the plasticizers currently available on the market are lacking a sufficient heat resistance, which has the consequence that the materials containing them under rapidly deteriorate under the conditions of use. The invention relates to therefore on the use of materials that, when added to typical commercial plasticizers the chemical and physical resistance of the latter significantly improve and the service life of the products to which they have been incorporated.

The advantages of the invention become more apparent when considering the following experimental data.

809 558/363

example 1

a) An oily polymer made from butadiene and styrene was produced according to the following recipe:

Parts by weight

Butadiene 80

Styrene 20

Petroleum hydrocarbons 10

Petroleum 190

Dioxane 30

Sodium 1.5

Isopropanol 0.3

Temperature 40 ° C

Complete conversion was achieved in 10 hours. The catalyst was destroyed and removed, and the product was treated and had in the manner described above until the non-volatile content reached 90% a viscosity of 1.0 poise at 50% non-volatile content. For the subsequent epoxidation were Peracetic acid solution and 200 g of a 50% solution of the polymer oil obtained in n-heptane in given a fluted 1-1 flask. The mixture was stirred vigorously for 28 hours at 20-27 ° C.

After the reaction had ended, the mixture was washed six times with 250 ecm of water each time, then the epoxide was taken up in dioxane and separated from the heptane. The epoxy was presented as a straw-colored, semi-solid material obtained by distilling off the dioxane in vacuo.

Three epoxies were made from oils with viscosities of 0.4, 0.7 and 1.5 poise (at 100% non-volatile Components). The products contained 2.11 percent by weight epoxy.

b) An oily polybutadiene made by sodium polymerization, a viscosity of 1.8 poise with 70% non-volatile components and a Staudinger molecular weight of about 3000 was dissolved in n-heptane to form a 50% solution. A sample of 200 g this solution was mixed with peracetic acid and reacted and worked up as under a).

c) The effectiveness of epoxidized oily polymer mixtures of diisooctyl phthalate according to the invention (= DIOP) is shown by the tests shown in Table I, in which a commercially available polyvinyl chloride resin came to use.

Polymer oils with viscosities of 0.4, 0.7 and 1.5 poise (100% non-volatile components) were made produced three epoxidized oils in the manner described. The epoxidized oils are used in the following Table I referred to as Samples 1, 2 and 3.

In preparing these test samples, 150 g of resin were mixed by hand with 3 g of sodium organophosphate

as a stabilizing agent and 1.5 g dibasic lead stearate dry mixed. 1 to 5 parts of other stabilizing agents per 100 parts of resin can be used in place of the sodium organophosphate. The dry mixture was heated in a beaker with 75 g of the epoxidized oily plasticizer and stirred to form a homogeneous mixture. This mixture was introduced into a 15.2 by 30.4 cm large laboratory roller mill heated with steam to about 140 to 160 ° C. The resin was then softened for about 2 minutes and milled on the roller for 5 minutes with occasional cutting. Qualitative tests showed that different combinations of vinyl resins and plasticizers required slightly different mill temperatures to achieve a good mixture within 5 minutes. After mixing in the roller mill, the material was obtained in sheets with a thickness of 1.9 to 3.8 mm,
ao In general, it was found that the new Phthalatestergemische invention high molecular weight vinyl resins in conventional rolling temperatures soften significantly faster or plasticizing as commercial phthalate plasticizers. This is important because it has long been known that prolonged exposure to heat during processing or later has a permanent adverse effect on the durability and physical properties of the vinyl resin. Therefore, the improved softening properties of the plasticized resin in which the new plasticizers are used make it possible to reduce the overall temperature treatment of the resin material.
The web material was then pressed at 140 ° C in a standard ASTM mold (D 16-41) into panels measuring 15.24 x 15.24 x 0.1905 cm. The pressing was carried out at 63 kg / cm ^{2 for} 10 minutes. The press plates were left to stand at 24 ° C. for at least 1 day before the examination.
The tensile strength was determined in the usual way in a "Scott tester" (model 3) at about 24 ° C. and 50% relative humidity. The speed at which the jaws moved apart was 50.8 cm / min. The aging due to the action of heat was measured in a hot-air circulation oven suitable for achieving reproducible results. The samples examined were cut out of the press plates with die C (ASTM D 412-41).
The dynamic modulus was determined by measuring the force occurring in a plasticized vinyl film under the conditions of 10% static deformation and 0.7% oscillatory deformation at 15 oscillations per second. The values are given in kg / cm ² - IO ⁴ . The results are given in Table I.

Table I.

Epoxidized polymer oil as a vinyl stabilizer

Composition of the vinyl mixture sample (Parts by weight) DIOP 1 2 3 Powdered homopolymer of polyvinyl chloride, Density 1.4 150 3 Dibasic lead stearate - 1.5

5 6

Table 1 (continued)

7! Ii en m inPTi QAtTim c Hf * r Viti vi mi ορΤιπηι »
ΙΛΟ al 11111 CLiaCli UlIg Uvl V Illj XllllaLfll Iittg sample (Parts by weight) DIOP 1 2 3 Plasticizers DIOP 75 71.25 71.25 71.25 Epoxidized polymer oil 3.75 3.75 3.75 Original properties Tensile strength, kg / cm ² 203.5 209.5 200.0 202.8 100% modulus, kg / cm ² 140.3 147.6 142.7 140.3 Stretch. ⁰ L 290 275 285 275 7 position aging at IUU C tensile strenght 164.8 181.4 185.2 191.9 100% module 154.2 170.4 172.8 167.0 strain 150 180 180 220 Z ₁ Iipfftsfip ^r Vftit 711 WioVpfiKIiphfirifi DftTitiiitiP " 81-52 87-52 93-63 95 - 80 volatility 7 days at ⁰ IOO C (loss of plasticizer in%) 15.7 13.5 17.2 13.0 Extraction by testbenzm 7 days at 52 ° C (loss of plasticizer in ° / ₀ ) 6.8 7.8 Dynamic module (kg / cm ² • IO ₄ ) + 25 ° 0.098 0.125 0.123 0.131 + 10 ° 0.323 0.422 0.429 0.408 - 5 ° 0.914 1,089 1.103 1.068 -20 ° 1,589 1,829 1,786 1,786

sample Used
Mixed poly
mer oil
0 ? Oise) Molecular
weight Weight percent
Epoxy
in the product DIOP 1 0.4 4000 2.11 2 0.7 6000 2.11 3 1.5 10,000 2.11

The data in Table I show that the replacement of 5 percent by weight diisooctyl phthalate with the epoxidized interpolymer oil reduces the volatility of the diisooctyl phthalate and its extractability by white spirit far more than one would expect solely from the replacement with a less volatile oil. The remarkable effect of the epoxidized polymer oil, however, is the greatly improved heat resistance of the vinyl compounds, which is indicated in the column "% tensile strength - remaining elongation". The two polymer oil samples with the lowest molecular weights (Samples 1 and 2) increase the heat resistance of the diisooctyl phthalate to a generally acceptable level. The polymer oil sample No. 3, which was obtained from the polymer having the highest molecular weight and containing the highest number of epoxy groups, greatly increases the heat resistance of the diisooctyl phthalate and is far superior to most of the commercially available plasticizers. Another advantage of using the epoxidized oil lies in the fact that it stabilizes the vinyl resins against the decomposition which occurs as a result of the elimination of HCl. Any elimination of HCl is easily recognizable, as the hydrogen chloride reacts with the lead oxide present to form PbCl _a , which makes the vinyl films opaque. In the above experiments, the films containing the epoxidized polymer had different transparency; this property was reinforced with an increasing number of epoxy groups. Sample 3, which contained the highest number of epoxy groups, was very clear; it follows that the formation of PbCl ₂ had been prevented.

Example 2

The effectiveness of the epoxidized oily polymers when added to diisooctyl phthalate is further increased shown in the test series shown in tables. In these trials the composition was the vinyl resin mixture and the method of processing the samples those of Example 1, c) identical. The values for test series A and B show that lower (2.5%) and higher concentrations (7.5%) of the epoxidized interpolymer oil of sample 3 somewhat in terms of resistance are less effective than the 5% concentration shown in Table I. It can be seen from this that the optimum concentration is when about 5% of the DIOP in the composition is epoxidized by the Polymer oil are replaced.

Row C data, Table II, shows that the epoxidized polybutadiene of Example 3 has resin resistances results that are roughly equivalent to those of the best epoxidized interpolymer blends, and that at the same time, it is decidedly superior in terms of its effectiveness as a plasticizer.

Claims (1)

TabeUe Π Composition of the vinyl mix
(Parts by weight) DIOP sample
A I B C. Powdered homopolymer of polyvinyl chloride,
Density 1.4 150 J - 1.5 Plasticizers
DIOP 75 73.13
1.87 ** 69.38
5.62 ** 71.25
3.75 *** Original properties
100% modulus, kg / cm ^a
Strain, % 203.9
138.5
300 203.9
138.1
305 201.8
136.7
315 199.6
133.9
305 Aged for 7 days at IOO ⁰ C
100 "/" module
% Tensile strength, residual elongation 174.7
164.5
150 '
85.7-50 178.5
165.5
175
87.8-57.4 199.6
177.5
235
99-74.6 199.3
175.4
235
99.8-77 Volatility after 7 days at ⁰ IOO C 17.5 16.8 18.7 20.5 Mineral oil extraction after 7 days at 52 ^° C 9.8 9.0 7.7 8.7 Dynamic module, kg / cm ² -10 *
+ 25 °
+ 10 °
- 5 °
-20 ° 1.015
0.330
0.872
1,582 0.110
0.387
0.991
1.709 0.136
0.429
1.083
1,877 0.113
0.387
0.998
1.765 The plasticizer mixture is used in amounts of about 5 to 100 parts, preferably 30 to 60 parts to 100 parts resin. The plasticized mixture itself consists of about 90 to 99% diisooctyl phthalate and 1 to 10%> preferably 5 ° / ₀ epoxidized hydrocarbon polymer. The polymeric materials that can be successfully plasticized with the esters according to the invention include the various vinyl resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, copolymers of vinyl chloride with vinyl acetate or vinylidene chloride, polyvinyl butyral or other polyvinyl acetates; Nitrocellulose, ethyl cellulose; rubbery polymers of diolefinic materials made from butadiene-nitrile (GR-A), butadiene-styrene (GR-S), or polychloroprene elastomers or isobutylene-diolefin copolymers of the GR-I type, or other polymers which are usually successfully plasticized. Mixtures of these classes of substances can be used, e.g. B. a mixture of 100 parts by weight of vinyl chloride resin and 10 to 300 parts by weight of synthetic butadiene-acrylonitrile rubber with 15 to 40 ° / ₀ nitrile. Of course, it should be noted that, in addition to the plasticizer, the polymer mixtures can also contain conventional stabilizers such as basic lead carbonate, sodium borate, oleic acid auxiliary plasticizers or plasticizers, fillers, pigments and, if the polymer is curable, also hardening agents. Claim: Use of epoxidized polymers containing 1 to 9.5 percent by weight of epoxy oxygen and from liquid polybutadiene or a liquid copolymer of at least 60 parts by weight Butadiene and up to 40 parts by weight of styrene have been obtained as an additive to it Ester plasticizers for solid polymeric organic plastics. 809 558/363 5.68 © Bundesdrocketei Berlin