DE941693C - Plastic masses made of polyvinyl chloride - Google Patents

Description

The invention relates to compositions of vinyl resins and phosphoric acid monoalkyl diaryl esters, in particular it relates to a mixture of polyvinyl chloride synthetic resins with the 5 phosphoric acid esters listed above. The designation "Polyvinyl chloride" includes not only polymerized vinyl chloride, but also mixed polymers of vinyl chloride · as well as mixtures containing both polymerized vinyl chloride and interpolymers Contained by vinyl chloride.

It is known per se to use phosphoric acid esters as plasticizers for polyvinyl chloride. So the use of tricresyl phosphate is known for this. In contrast, the phosphoric acid monoalkyl diaryl esters the following advantages:

With the same content of plasticizer, those produced from the mixtures of the polymers are Articles pliable to much lower temperatures if a monoalkyldiarylphosphate ester instead of the tricresyl phosphate as an additive is used. In addition, the monoalkyl diaryl phosphate esters are virtually non-toxic, and Films of polyvinyl chloride blends in which these esters are used as plasticizers can be used for food packaging, which is the case with films made of polyvinyl chloride, plasticized with tricresyl phosphate is not the case.

The following examples illustrate the beneficial and unexpected results that

through the use of monoalkyldiarylphosphoric acid esters in polyvinyl resin compositions, but the invention is not intended to refer to or be limited by the examples.

Example -i

3 parts by weight of polyvinyl chloride were added

"" 2 parts by weight Phosplhorsäure-2-ä.thylhexyldipihenylester, until a homogeneous mixture was achieved as a plasticizer intimately mixed and then worked in a Friktionswalzwerk with a ⁰ 140 hot roll. A layer of the mixture was cut from the roller and cooled. A portion of this was formed in a hydraulic press at 163 ^° into a plate 1 mm thick. After removal from the press, the examination of the samples showed the following values:

Low temperature

Cohesion point ........ - 41 °

Volatility 5.8%

Flammability not flammable

Abrasion Resistance 75

Oil resistance 5%. .

The results of this example show that phosphoric acid-2-ethylfaexy ldipbenyl ter as a softener Polyvinylchloride mixtures containing a number of desirable properties of such Weiphmacherhaltiger mixtures have, namely ■ 30 good low-temperature flexibility, low Loss of plasticizer through volatilization and non-flammability. It also draws This blend is characterized by increased resistance to oil absorption, which is highly desirable and quite unexpected, otherwise plasticizers, which have good low-temperature flexibility give, at the same time lead to low oil resistance. It was also shown that the abrasion loss' was only about half the size of that of a phthalic acid diocty ! Ester-, sebacic acid dibutyl ester or phosphoric acid tricresyl ester containing as plasticizer Polyvinyl chloride mixture.

Example 2

3 parts by weight of a copolymer of vinyl chloride and vinyl acetate (bound vinyl chloride about 94 weight percent) decyldiphenylester Phosphoirsäuire-n-intimately mixed with 2 parts by weight as the plasticizer and anschJießend worked 'in a Frikfcionswalzwerk with a 140 ⁰ hot roll "is reached until a homogeneous mixture. A part of it was pressed in the form of a 1 mm thick plate. Examination of this sample gave the following values:

Low temperature

Flexibility point -41 °

Volatility 1.7%

Flammability not flammable

Abrasion Resistance 89

Oil resistance 14.6%

The same desired result was obtained: good low temperature flexibility, less Loss through. Volatility and non-flammability. Even if the value of the oil absorption increased, it was still considerably below the values which is achieved when using conventional plasticizers which impart good low-temperature flexibility will. The superiority in terms of abrasion resistance was also shown again.

Example 3

3 parts by weight of polyvinyl chloride are mixed intimately with 2 parts by weight Phosp'horsäurelauryldiphenylester and then worked in a fric- "tidnswalzwerk with a 140 ⁰ hot roller until it reaches a homogeneous mixture. A part of it was pressed in the form of a 1 mm thick plate and gave the following values:

Low temperature

.Flexibility point —44 ⁰

Volatility 1.4% '

Flammability not flammable

Abrasion Resistance 72

oil resistance 15.4% ^8s

Here, too, it can be seen that the plasticizer of the polyvinyl resin mixture alone also has one good flexibility at low temperatures, low loss of plasticizer due to volatilization and non-waste be given flammability. Even if the oil absorption value increased, it was even lower or at most equal to the good low-temperature BJegsanikeit when using the usual imparting plasticizer is achieved. In addition, these examples show how extremely beneficial the use of 2-ethylhexyldiphenyl phosphate as a plasticizer.

Example 4

3 parts by weight of polyvinyl chloride Phasphorsäure-2-äthylhexyldikresylester intimately mixed with 2 Gewichitsteilen and then worked in a rolling mill at 140 ⁰ until it reaches a homogeneous mixture. A ι mm thick plate formed from it gave the following values:

Low temperature flexibility point ■ - · 42 ⁰

Volatility, 2.1%

Flammability not flammable

Abrasion resistance 74

Oil resistance 10%

The improvement achieved, the low low-temperature flexibility of the film, is far below those achievable in polyvinyl chloride resin mixtures with phosphoric acid tricresyl ester as plasticizer Values. In addition, it was shown again that the plasticizer alone also provides good low-temperature flexibility, low volatilization loss and non-flammability achieved became.

Example 5

3 parts by weight of polyvinyl chloride are mixed with 2 parts by weight of phosphoric acid-2-methylpentyldi-

until it reaches a homogeneous mixture cresyl intimately mixed and then worked in a rolling mill at 140 ^0th A ι mm thick plate formed from it gave the following values:

■> low temperature

Flexibility Point —29 ⁰

Volatility 6.4 ^p / o

Flammability not flammable

Example 6

3 parts by weight of polyvinyl chloride are with

Until it reaches a homogeneous mixture of 2 parts by weight of a Phosphorsäurenonyldiphenylesters intimately mixed and then worked in a rolling mill at 140 ^0th A ι mm thick plate formed from it gave the following values:

Low Temperature Flexibility Point -27 ⁰

Volatility 6,3%

Flammability not flammable

Example 7
3 parts by weight of polyvinyl chloride are with

Until it reaches a homogeneous mixture of 3 parts by weight of a Phosphorsäurenonyldiphenylesters intimately mixed and then worked in a rolling mill at 140 ^0th A ι mm thick plate formed from it gave the following values:

Low temperature

Flexibility point -43 °

Volatility 7.9%

Flammability not flammable

Example 8

7 parts by weight of polyvinyl chloride are mixed intimately with a Phospnorsäurenonyldiphenylesters 3 parts by weight, and then worked in a rolling mill at 140 ⁰ until it reaches a homogeneous mixture. A ι mm thick plate formed from it gave the following values:

Low temperature

Flexibility point · -6 °

Volatility 4.3%

Flammability not flammable

Example 9

3 parts by weight of polyvinyl chloride are mixed intimately with 2 parts by weight Phosphorsäureisooctyldiphenylester and then worked in a rolling mill at 140 ⁰ until it reaches a homogeneous mixture. A ι mm thick plate formed from it gave the following values:

Low temperature

Flexibility point - ■ 34 ⁰

Volatility 7.2%

Flammability not flammable

Example 10

3 parts by weight of a copolymer of vinyl chloride and vinylidene chloride (bound vinyl chloride about 92 percent by weight) are mixed with 2 parts by weight of a Pnosphoarsäurenonyldiphenylesters (whose Nonylradikal of a trimethyl-hexyl alcohol derived) intimately mixed and then worked in a two-roll Friktionswalzwerk with a 140 ⁰ hot roller until a homogeneous mixture achieved iist. The plate pulled off the roller gave the following values:

Low temperature

Flexibility point below - 30 ⁰

Volatility about 6 ° / o

Flammability not flammable

Example 11

3 parts by weight of polyvinyl chloride are added

2 parts by weight Phosphorsäureisooctyldikresylester intimately mixed and this mixture is worked through a rolling mill at 140 ⁰ until it reaches a homogeneous mixture. The plate withdrawn from the roller was then molded according to the procedure of the previous examples. The physical properties of the molded sample thus obtained were then essentially the same as those of the sample prepared in Example 4, which is from

3 parts of polyvinyl chloride and 2 parts of phosphoric acid 2-ethylhexyldicreisyl ester consists.

Other copolymers of vinyl chloride can also go with the phosphoric acid monoalkyldiaryl esters of the invention are plasticized as plasticizers, iso especially copolymers from 95 to 85 percent by weight vinyl chloride and 5 to 15 percent by weight vinylidene chloride, maleic acid diethyl ester or methyl methacrylate.

Claims (3)

PATENT CLAIMS: 1. Plastic corns consisting of polyvinyl chloride made of polyvinyl chloride or copolymers mainly containing polyvinyl chloride, and a phosphoric acid monoalkyldiaryl ester of the formula O Il R - O - P - (0 - R ₁ J ₂ in which R is an alkyl radical with at least 6 and not more than 12 carbon atoms and R _{1 is} phenyl or KJresyl as plasticizer. 2. Plastic mass according to claim 1, characterized in that it contains 5 to 60 percent by weight, preferably 20 to 60 percent by weight, phosphoric acid monoalkyl diaryl ester. 3. Plastic mass according to claim 1 or 2, characterized by a content of Monoalkyldiarylphosphorsäureester, Phosphorsäureoctyldiphenylester, Phosphorsäureisooctyldiphenylester, Phosphorsäu ^{i re-i} 2-ethyl hexyldipihenylester, Phoisphorsäureoctyldikresylester, Phosphorsäureisooctyldikresylester, phosphoric acid-2-äthylhexyldikresylester. Phosphoric acid n-decyldiphenyl ester, phosphoric acid lauryldiphenyl ester, phosphoric acid onyldiphenyl ester, phosphoric acid 2-methylpentyldicresyl ester. © 509 690 4.56