DE2349705A1 - STABILIZER FOR RESIN - Google Patents

Description

Stabilizer for synthetic resins

Lead salts are widely used as stabilizers for vinyl resins. This includes the basic lead salts inorganic acids to non-lubricating stabilizers and lead salts or soaps to organic Acids, e.g. lead stearate, to the lubricating stabilizers. These compounds are poisonous and accordingly will you. often in the form of granules mixed with a plasticizer, supplied to the development to prevent harmful dust when the stabilizer is introduced into the resin. Will such granules used to make solid PVC-polyvinyl chloride) compounds To stabilize the amount of material, mostly a plasticizer, which acts as a binder to bind the powdery Lead salt used on the granules is kept to a minimum. However, it has been shown that a stabilizer granulate, even if there is only a small proportion of a liquid or solid binder with low Melting point, such as DAP (dialphanyl phthalate), reduces the softening point of solid PVC, which is sometimes a disadvantage.

509817/1117

BANK »HYPO-BANK, β MÜNCHEN 2, THEATINERSTR. 11, ACCOUNT NO. 3 437 370 POST CHECK ACCOUNT) MÖNCHEN 15 453

The invention now provides a stabilizer for vinyl resins, which consists of a granulate of particles of a basic lead salt of an inorganic acid, which are bound by a liquid binder formed from a fatty acid in granular form, this fatty acid being liquid at room temperature and ten or more carbon contains atoms, and from a mixture of fatty acids that contain no more than * tQ Ge \ f .-% of acids with eight or fewer carbon atoms or a liquid phenol. The granules can also contain an organic acid lead soap.

The amount of binder included must be sufficient to make the powdery basic lead salt in granulate form tie. However, it should not be so large that a sticky product is formed. It depends on the particle size of the basic lead salt and it is generally between 5 and 20 wt .- ^ of the powder.

The liquid used can be a mixture of liquids and preferably has a melting point below 25 ° C. However, it can have a higher melting point, provided that it becomes liquid when heated, to create liquid bridges between the individual lead salt particles and thus to effect granulation.

The liquid should also be such that it produces granules that are readily distributed in the resin. A liquid that meets the requirements is isostearic acid, a liquid isomer of stearic acid with a melting point of about 9 ⁰ C. We have found that a granulate of the tripartite lead stearate, which contains isostearic acid as a binder, actually increases the softening point of the rigid PVC.

509817/1117

The binding liquid reacts with the basic lead salt of the inorganic acid when the granules are formed or during the manufacture of one containing the granules PVC moldings. In contrast to the other binders normally used, such as oils, waxes and Plasticizers, the reaction product does not cause any reduction in the softening of the PVC moldings after it have been treated.

Another suitable liquid is oleic acid. The isostearic acid is expensive and other liquids possible are fatty acids with a low melting point, such as palm kernel, nutmeal and coconut acids and mixtures of these acids with liquid acids, such as isostearic, oleic or Al / 2 acids, the latter a mixture of about 45 wt .- ^ octo-acid, 45 wt .- ^ Deco Acid and 10 wt- $ lauric acid is.

Suitable liquid phenols are P-nonylphenol and a Mixture of ortho-, meta- and paracresol from Coalite Limited.

In the examples below, in which the Components are expressed in percentages by weight the stabilizer made from a mixture of tribasic lead sulphate and lead stearate. The invention however, other basic lead salts of inorganic acids, such as white lead, are dibasic lead phosphate and tetra-basic lead sulfate, alone or mixed with lead stearate or other lubricating agent Stabilizer applicable.

Granules were made by mixing 450 grams of tribasic Lead sulfate powder, 45 g normal lead stearate and 40 g of a binder liquid in a cold laboratory kneader, with the mashing continued

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until the powder was dust-free.

Each dust-free mixture was pressed through a 2mm press, to form cylindrical granules.

TABLE I Liquids used for the production of granules

Surname

A OK / 2

composition

Mixture of approximately 45% by weight Octo acid, 45% by weight deco acid and 10% by weight of lauric acid.

Isostearic acid

(Unilever Emery Ltd) A liquid isomer of stearic acid with branched chains of carbon atoms.

Oleic acid

A liquid unsaturated acid with straight chains of the C atoms.

Ground nut fatty acid) palm kernel fatty acid) coconut fatty acid) acids produced by distillation from crude fatty acids produced by acid hydrolysis of the vegetable oils mentioned have been won.

Mixed cresols
(Coalite Ltd)

Topanol A

A mixture of ortho-, meta- and para-cresol.

An alkylated hydroxyoluene,

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Manufacture of solid PVC panels composition

Corvic D60 / II polymer - 100 pts / wt

Normal lead stearate - 0.7 pts / wt

Dibasic lead stearate - 0.4 pts / wt

Wax E - 0.4 pts / wt

Wax PA 190 - 0.1 pts / wt

Calcium stearate - 0.4 pts / wt

Stabilizer y 3.6 pts / wt

(Powder and granules)

Isostearic acid and DAP granules were also used in an amount of 5, ^ pt / lOO PVC, ·,

The mixture was mixed on a roller mill at 160 ° C for five Milled for minutes with shear and five minutes without thrust. The ground leaf became one

2
Pressed plate 12.5 cm and 2.5 mm thick. The sheet was placed in a window mold for two minutes at 160 ° C. under slight pressure and for three minutes under a

Pressed a pressure of 236 kp / cm and still cooled under pressure.

Try PVC

1. Vicat softening point BS 2782: 1965 method 1025.

A cylindrical rod with a tip of 1.00 mm in cross section was placed on a sample and loaded with a 5 kg weight. The trial sample was placed in a glycerine and the temperature is raised at a uniform rate of 50 + 5 ° C per hour, was of a temperature 5O ⁰ C below the expected softening point of the Mate • rials. As soon as the tip of the rod penetrated 0.1 mm into the sample (measured with a micrometer

5098 17/1 117 - 6 -

Dial gauge) the temperature was recorded.

2. Heat resistance

The heat resistance of the pressed PVC was measured by means of of the oven aging and Congo red test.

3. Brabender Plastograph Test

100 g of Vinatex polymer were mixed with 3 g of granules in a Kenwood mixer for two minutes. 35 g of the mixture were rpm in Plastograph at 70 and tested 190 ⁰ C in a measuring head of the type 30th Torque readings were taken as an indication of the liquidity of the melt and the disintegration time was also recorded.

Dispersibility

The dispersibility of the granules in the PVC was determined by rolling the granules with PVC and DAP to a very highly plasticized PVC sheet underneath Conditions that require a minimum of labor and heat.

In practice it has been proven that a granulate that disperses a maximum of 0.5 particles / 6.45 cm is

Bonding of solid and plasticized PVC is acceptable is.

» TABLE II

Recovery and dispersibility of the granulate

... dispersible—

State of the appearance of the «particle /

Liquid premix granules inches

Isostearin
acid dust free long , well shaped O, 05 Oleic acid dust free long , well shaped O, 15th Palm kernel fat
acid dust free Well shaped 0, 05

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liquid

Dispersible

Condition of the appearance of the particle / premix granulate inch

Coconut fatty acid

ground nut fatty acid

dust-free well formed dust-free well formed

Mixture of coconut and coconut fatty acids, long, dust-free, well formed
with 15 $ oleic acid

Coconut fatty acids with ± 5% isostearic acid

dust-free long,

Coconut fatty acids with 15% AlOl / 2-acid dust-free long, mixed cresols dust-free Topanol A dust-free 0.08 0.22

0.05

Well shaped 0.10 Well shaped 0.05 Well shaped 0.12 Well shaped 0.25

In the dispersion test, it was seen that the dispersibility of the granulate was excellent.

TABLE III Vicat softening points

Granulate determination
⁰ C

average

Tri-base lead sulfate and Lead stearate powder (control) 3.6 particles / 100 V.C.

Isostearic acid oleic acid palm kernel fatty acid coconut fatty acid Ground nut fatty acid

Palm kernel fatty acid + 15% oleic acid 83.5 84.0

83, ^ 83.6

83.8

84.4 83, 8th 84.1 83.2 82, 8th 83.0 83.5 " 83, 5 83.5 83.8 83, 6th 83.7 83.6 83, 4th 83.5

83.5

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granules

Determination of average C C

Coconut fatty acid
+ 15% Al01 / 2 83.7 83.4 83. 6th Coconut fatty acid
+ 15% isostearic acid 83.3 83.8 83. 6th Mixed cresols 83.6 84.4 84. 0 TopanolA 83.6 83.5 83. 5 Isostearic acid
(5/4 pts / 100 PVC) 83.2 83.4 83. 3 control
(5.4 pts / 100 PVC) 83.6 83.5 83. 5

The control sample in the table above consisted only of tribasic lead sulfate and lead stearate powders without Binder liquid. As can be seen, the softening point became significantly decreased once oleic acid was used, whereas no significant decrease with the other binders was observed. On the contrary, the granules bound with isostearic acid actually yielded an increase in the softening point.

TABLE IV Heat Resistance

granules

Oven aging at 180 ° C Congo red time 0 hours 1 hour 2 hours at 180 ° C

Tri-basic lead
sulfate powder (con
trolls) White
similar leather-
Colours leather-
Colours 3 Hours 50 minutes Isostearin & acid ti Il Il 3 Hours 50 minutes Oleic acid η Il Il 4th Hours 15 minutes Palm kernel fatty acid ti Il Il · 4th Hrs. 25 min. Coconut fatty acid Il Il Il 4th Hours 20 minutes Ground nut fat
acid η ti Il 4th Hours 15 minutes

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r 9 -

_ 9 -

Oven aging at 180 ° C Congo red time

Ο hours 1 hour 2 hours at 180 ^° C

Palm core fatty acid white- leather- leather- 4 hrs. 25 min.

+ ± 5% oleic acid similar colors colors

Coconut fatty acid

+ 15% AlOl / 2-acid """3 hours 50 min.

Coconut fatty acid

+ 15% isostearic acid " tr Il 3 Hours. 50 Min. Mixed cresols " Il Il H Hours. 10 Min. Topanol A yellow polish
yellow It 4th Hours. 10 Min.

In this table, the Congo Red time is the period of time that passes before the evolution of hydrogen chloride begins.

TABLE V

Brabender Plastogr a ph results

Torque Disintegration Time Granules (Meter Gram) (Minutes)

Tribasic lead sulfate powder (control) 1950 12

Topanol A 1950 11

Mixed cresols 195 ° 9 1/2

Isostearic acid 1950 11

The invention comprises a change in the above-described granules resulting from a surprising discovery results in that. can be seen from the accompanying drawing. This graph shows the effect on the Vicat softening point of PVC by adding very small amounts of liquids to PVC, which are generally included in PVC are used in much larger quantities as plasticizers, extenders for softeners or as liquid lubricants. at

- 10 509817/1117

Addition of larger amounts leads to all these liquids to a substantial lowering of the softening point. The three liquids tested were dialphanyl phthalate (DAP), a plasticizer completely compatible with PVC, Riosella oil, a liquid paraffin that is completely incompatible with PVC and acts as a liquid lubricant and Cereclor S45, a chlorinated hydrocarbon that is partially compatible with PVC.

As can be seen, the addition of 0.1 wt% yielded each of these liquids to PVC an increase in the softening point, whereby this softening point began to decrease, when the liquid addition is over about $ 0.2 in the case of Cereclor S.45 and Rissella Oil and over about 0.25% in the case of DAP was increased.

For this reason, the invention envisages an exchange of one Part of the binder liquid in the previously described Granules with a plasticizer, a chlorinated hydrocarbon or a liquid lubricant for PVC in an amount that increases the softening point of a solid PVC molding, the has been stabilized by granules, results. Unfortunately it is not possible to get the exact amount of in the granules Specify the liquid to be introduced because, since the granulate is mainly used to protect the PVC against degradation to protect by heat during the manufacturing process, the amount of granulated stabilizer that is used by a plastics manufacturer is used, on the nature depends on the manufacturing equipment available. Generally speaking, it lies Amount of granulated stabilizer between 1 and 5 parts by weight per 100 parts of resin. As a general On average, 3.6 parts by weight of granulate can be considered sufficient and, on this basis,

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leads to the uptake of about 4 wt .- ^ one of the above Liquids in the granules under normal working conditions cause an increase in the softening point of the PVC.

The presence of such additional liquid in the granules still has the desirable effect that, since they the. Fatty acid or the phenol dilutes the likelihood is not so great that during the manufacture of the granules as a result of an excess Reactivity between the fatty acid and the basic lead salt form particles of difficult to disperse material.

Further examples are given below which demonstrate the effect of the granulate according to the invention on the Vicat softening point of solid PVC show. In these examples the proportions are given by weight. Different Quantities of the stabilizer granules of the aforementioned compositions were added to solid PVC moldings, to create a compound of the following final composition:

PVC polymer Corvic D56 / 11 100

Granules A-N - different

Lead stearate - 0.8

Dibasic lead stearate - 0.4

Wax E - Oi4

W _a chs PA 190 - 0.1

Calcium stearate - 0.4

The final composition showed in all cases a content of 0.8 parts lead stearate and a vioat softening point of 82.7 ° C after stabilization with dry tribasic lead sulfate. Since in the case of the granules C-N

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some lead stearate by reaction of the basic lead salt of the organic acid and the PKCN fatty acid (a mixture

from palm kernel and coconut oil fatty acids),

the specified amounts of lead stearate were put into the PVC molding introduced to the final lead stearate content to bring it down to 0.8 parts.

Composition of the granules

A tribasic lead sulfate - 500

Dialphanyl phthalate - 25

Paranonylphenol - 25

B tribasic lead sulfate - 500

Dialphanyl phthalate - 12.5

Paranonylphenol - 37.5

C tribasic lead sulfate - 450

Cereohlor p.52 -

PKCN fatty acid. - 42.5

D tribasic lead sulfate - 450

Cerechlor pp 52-15

PKCN fatty acid - 35

E three base raw lead sulfate - 450

Dialphanyl phthalate - 12.5

PKCN fatty acid - 37.5

F tribasic lead sulfate -

Dialphanyl Phthalate - 25.0

PKCN fatty acid - 25.0

G Four base lead sulfate - 500

Cerechlor p.52. -

PKCN fatty acid - 42.5

H fourbasic lead sulfate - 500

Cereohlor p.52 - 15

PKCN fatty acid - 35

- 13 -

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Tetra-basic lead sulfate - £ 00

Dialphanyl Phthalate - 12.5

PKCN fatty acid '' - 37.5

J Four-basic lead sulfate - 500

Dialphanyl Phthalate - -25 '

PKCN fatty acid '- 25

K. Two-base phosphorous acid

Lead salt - 500

Cerechlor p.52 -

PKCN fatty acid - 42.5

L Dibasic phosphorous acid

Lead salt - 500

Cerechlor pp 52-15

PKCN fatty acid '~ 35

M Dibasic phosphorous acid

Lead salt - 500

Dialphanyl phthalate _r 12.5

PKCN fatty acid .. - 37.5

N Dibasic phosphorous acid

Lead salt ■ -, 500

Dialphanyl phthalate - 25

PKCN fatty acid -. 2.5

The following table shows the quantities of various

Granules and lead stearate that were added in various tests and the Vicat softening points achieved. ^l

granules ; and 3 Average I.
- 14 - Lead stearate content turned lot 3 Vicat softening p. 0.8 Type a 3.6 3 .82.7 ⁰ C 0.8. Type, A 1.8 3 ■ 83.4 ⁰ C • ^: 0.8 Type B 3.6 1 1 17 . 83.2 ⁰ C- . · 0.8 '·. Type B 1.8 83.7 ⁰ C 0.61 C. 5. . 82.7 ⁰ C 0.65 D. 5. . 83.7 ° 0 0.63 E. 5. 83..9 ° C 0.71 F. 5. 83.7 ° C 5098 yiI

23A9705

Granules and average lead stearate content used amount of Vicat-Erweiohungsp.

0.66 F. 5.3 83.9 ° C 0.40 C. 3.6 83.7 ° C 0.47 D. 3.6 83.1 ° C 0.44 E. 3.6 83.5 ° C 0.56 F. 3.6 82.9 ° C 0.40 G. 3.6 83.4 ⁰ C 0.47 H. 3.6 .82.5 ⁰ C 0.44 I. 3.6 82.9 ° C 0.56 J. 3.6 82.8 ⁰ C 0.40 K. 3.6 82.7 ⁰ C 0.47 L. 3.6 83.5 ° C 0.44 M. 3.6 83.6 ⁰ C 0.56 N. 3.6 82.6 ° C

As can be seen from this, the Vicat softening point was in all cases at least 82.7 ° C, this value being achieved using dry tribasic lead sulfate powder, and in many cases this value
was exceeded.

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Claims (9)

Claims 1. Stabilizer for vinyl resins, characterized by granules containing particles of a basic lead salt of an inorganic acid, which are bound in granular form by a liquid binder of a fatty acid which is liquid at room temperature and contains ten or more carbon atoms, and a mixture of fatty acids that not more than 40 wt -.% acids with eight or less carbon atoms or a liquid phenol. 2. Stabilizer according to claim 1, characterized in that the granules also contain an organic lead soap Contain acid. 3. Stabilizer according to claim 1 or 2, characterized in that the amount of binder in the granules between 5 and 20% of the basic lead salt in the granules amounts to. 4. Stabilizer according to one of claims 1 to 3, characterized characterized in that the binder has a melting point below 25 ° C. 5. Stabilizer according to one of claims 1 to k, characterized in that the binder is a PKCN fatty acid. 6. Stabilizer according to one of claims 1 to 4, characterized characterized in that the binder is a paranonylphenol. 7 »Stabilizer according to one of claims 1 to 6, characterized characterized that the granules as part of the binder - 16 509817/1 117 - Io - liquid a plasticizer, a chlorinated carbon. hydrogen or a liquid lubricant for the PVC in an amount sufficient to reach the softening point of a solid PVC molding. 8. Stabilizer according to claim 7, characterized in that the granules contain about h wt .-% plasticizer, chlorinated hydrocarbon or liquid lubricant. 9. Stabilizer according to claim 1, characterized in that it has a composition according to one of the described Has examples. 5098 1771 117.