DE1040789B - Process for the production of polymers and copolymers - Google Patents

Description

The invention relates to a process for the production of polymers and copolymers from vinylene carbonate. A particular embodiment of the invention relates to the manufacture of an improved polyethylene-like Materials.

According to the invention, vinylene carbonate is polymerized either alone or together with other unsaturated organic compounds which can be copolymerized with it, in particular ethylene, at pressures of at least 350 kg / cm ² . According to a particular embodiment, vinylene carbonate alone or with mixed monomers is polymerized at pressures of at least 1015 kg / cm ² and preferably at pressures within the range from 1400 to 2800 kg / cm ² . A copolymerization of vinylene carbonate with ethylene, styrene, acrylonitrile, methyl methacrylate or other mixed monomers also takes place at high pressures, namely at at least 350 kg / cm ² .

The properties of vinylene carbonate and processes for its preparation are from Newman and Addor, Journ. Amer. Chem. Soc, 75, p. 1263, March 5, 1953. Vinylene carbonate has the structural formula :

HC =

.0

(T

A suitable process for the production of vinylene carbonate is the chlorination of ethylene carbonate Monochlorethylene carbonate with subsequent dehydrochlorination of this compound by reaction with a Amine, resulting in vinylene carbonate.

The process according to the invention is opposed to polymerization of vinylene carbonate usually Numerous advantages of pressure, namely: significantly higher rate of polymerization; smaller amounts of required catalyst; greater homogeneity the copolymers; better compatibility of the copolymers of vinylene carbonate with other polymers Materials; ester polymers as a result of increased Molecular weight; Polymerization can be carried out at considerably lower temperatures; higher conversion percentage to polymer.

While certain advantages are obtained at pressures of 70 to 350 kg / cm ² , the pressure should be at least 350 kg / cm ² for best results. Pressures of at least 1050 kg / cm ^{2 are} preferably used. Often, optimal results are achieved at pressures within the range of 1400 to 2800 kg / cm ² . There is no particular upper pressure limit, there are methods of manufacture

of polymers
and copolymers

Applicant:

Monsanto Chemical Company,
St. Louis, Mo. (V. St. A.)

Representative: Dr. E. Wiegand, Munich 9,

and Dipl.-Ing. W. Niemann, Hamburg 1,

Ballindamm 26, patent attorneys

Claimed priority:
V. St. v. America May 18, 1953

Earl William Gluesenkamp

and John Douglas Calfee, Dayton, Ohio (V. St. A.]
have been named as inventors

Pressures up to 14,000 kg / cm ² or even higher are suitable. The high pressures which can be used according to the invention do not form any barriers to the technical application of the method.

The polymerizations can be carried out at temperatures within a rather wide range, which preferably ranges from 35 to 125 ⁰ C. At the higher temperatures there is a tendency to form a discolored product, probably due to the decomposition of vinylene carbonate. In the case of the rapid polymerization and sufficient heat dissipation that can be achieved according to the invention, there is a considerable tolerance with regard to the temperatures. In any case, a sufficiently high temperature should be used in order to obtain a good reaction rate. The preferred temperature range is between 50 and 10O ⁰ C.

The effect of relatively high temperatures is illustrated below. Of styrene were placed in a high-pressure Schüttelbombe g in an amount of 80 g and vinylene carbonate in an amount of 20, and the bomb was cooled in dry ice (solid CO _2), evacuated and then heated to 12O ⁰ C. The bomb was pressurized to 350 kg / cm ² with water and the pressure was increased to 1750 kg / cm ² in 350 kg / cm ^{2 increments at half hour intervals.} At the latter pressure, the reaction was too rapid and the pressure was therefore reduced to 1400 kg / cm ² . the

8Ϊ3 657/452

3 4

Bomb was kept at 120 ^° C. and 1400 kg / cm ² pressure during vinylene carbonate with one or more polymers for a total of 25 hours. The temperable compounds with the non-aromatic temperature were finally increased for a short time to)> C = C <(- group, for example with unsaturated monomers, 190 ° C, in order to achieve the most complete polymer possible Unsaturation can be obtained from a single ethylation of the remaining monomer.A test end group can be attributed to a negative function of the product produced in this way Was, probably as a result of a copolymerization of vinylene carbonate with vinylidene, excessive heat build-up in and near the middle of the compounds, including vinyl compounds, reaction mass, since part of the polymer bound a dark decomposition product in the middle, as well as acrylyl and alkacrylyl compounds and with the section of the bomb applicable, which contained a single polymerizable, mix. The product was otherwise useful have ethylene group. A mixed-The same polymerization can be carried out without generating the polymerization is also with polymerizable compounds material that can be carried out with fertilizers that work with a majority of ethylene, slightly milder temperature conditions, broken down with aliphatic character, regardless of ^{e.g. 90:} C and 1400kg / cm ² or at 8O ⁰ C and 15 whether these are conjugated or isolated. A particularly 2800 kg / cm ² . In the same way, the mixed polymeric preferred class of mixed monomers which can be very satisfactorily mixed with vinylensation of vinylene carbonate with ethylene at pressures in carbonate according to the process according to the invention in the vicinity of 1050 kg / cm ^{2 is that of poly-50} up to 75 ⁰ C in front of you. merisable unsaturated compounds, in which a particularly important embodiment of the invention the unsaturation at terminal methylene groups occurs and is the production of copolymers of ethylene with vinylene carbonate can be represented _{by a CH 2 = C (^ - group} with a terminal methylene group obtained from a polyethylene-like material which, in terms of interpolymerization with vinylene carbonate, is superior to the best technical pressures according to the process according to the invention in terms of copolymerization with vinylene carbonate at high some of its properties among polyethylenes is not easy, for example olefinic hydrocarbons such as ethylene, even the best technical polyethylenes leave something to be desired in their propylene, isobutylene, pentene, acrylic and alkacrylic physical properties, especially compounds such as acrylic and haloacrylic -, Meths special They often do not have sufficient surface acrylic, ethacrylic, etc. acids, esters, nitriles and amides, surface gloss and insufficient clarity. 30 z. B. acrylonitrile, methyl methacrylate, methyl ethacrylate, the copolymerization of ethylene with vinylen ethyl methacrylate, butyl methacrylate, octyl methacrylate, carbonate can be carried out under conditions that cyclohexyl methacrylate, methoxymethyl methacrylate, usually lead to a cross-linked polyethylene with cross-n-butoxyethyl methacrylate, n-butoxyethyl methacrylate, n-butoxyethyl methacrylate, that for technical use acrylate, aminoalkyl methacrylate, such as /? - diethylamino is unsuitable. According to the invention, however, a polyethylene-like acid, methacrylamide, ethyl acrylate and a-chloroacrylic material can be produced by the 35 ethyl methacrylate, chloroethyl methacrylate, methacrylic copolymerization, the excellent physical acid; Vinyl and vinylidene halides, such as vinyl chloride, has properties including a low elasticity of vinyl fluoride, vinylidene chloride, vinylidene fluoride, 1-fluorine after-effect, and which is very stable to heat. 1-chlorethylene; Vinyl carboxylates, such as vinyl acetate, vinyl-The copolymer is much clearer and has a significantly better surface gloss than polyethylene acetate, vinyl propionate, vinyl benzoate and vinyl stearate; itself. N-vinylimides, such as N-vinylphthalimide and N-vinyl-Die copolymers can advantageously be 5 to succinimide; N-vinyl lactams, such as N-vinyl caprolactam, 99 percent by weight ethylene and 95 to 1 percent by weight, and N-vinyl butyrolactam; Vinyl aryls, such as styrene carbonate, vinylene carbonate, based on the total weight of the monomers, entstyrenes and vinylnaphthalene entering into 45 α-methylstyrene, ring-substituted methylstyrenes, chlorine, the copolymer; and other vinyl derivatives, but smaller amounts such as methyl vinyl ketone, vinyl pyridine, 2-methyl-5-vinyl one of the components (up to 1 percent by weight or pyridine, 2-vinylthiophene, vinylpyrrolidone, vinylcarbczol, including) can also be used. Vinyl isobutyl ether and vinyl ethyl ether.

Ethylene-vinylene-50 polyfluoroethylene of the general formula CF ₂ = CXY are of particular importance

carbonate copolymers with a larger Ge (in which X stands for H, Cl or F, and Y stands for Cl or F),

percentage by weight of ethylene compared to vinylene carbonate. which as mixed monomers with vinylene carbonate

You can use a usually solid polymer can be turned from, include tetrafluoroethylene,

achieve high molecular weight. Suitable proportions of chlorotrifluoroethylene, trifluoroethylene and 1,1-dichloro

for the production of polyethylene-like products are 55 2,2-difmoräthylen ein.

about 1 to 30 percent by weight vinylene carbonate, based on specific examples of copolymers based on the total monomeric material. Particularly good results are obtained when the process according to the invention was achieved with 20 percent by weight of vinylene in mixtures of vinylene carbonate with other carbonate. Compounds with olefin bonds are used. The copolymerization of ethylene with vinylene-60 are inter alia: vinylene carbonate-ethylene, vinylene carbonate is expediently carried out at temperatures between carbonate-vinyl chloride, vinylene carbonate-ethylene-Vi-35 to 125 ^° C. The preferred range is 50 to 100 ⁰ C. Nyl chloride, vinylene carbonate - tetrafluoroethylene, vinyl - At higher temperatures there is a certain tendency of carbonate - vinylidene chlorofluoride, vinylene carbonate - to form a discolored product. It is a particular advantage of the invention that such moderate temperatures can be used with isobutylene, vinylene carbonate-acrylonitrile, vinylene carboratures and still mixed nat-acrylonitrile-vinylpyridines, especially those which are obtained as polymers. which contain easily processable 2 to 10% vinylpyridine, vinylene carbonate - isosind, butylene - vinylidene chloride, vinylene carbonate - vinyl ace - The process according to the invention also has, vinylene carbonate - vinyl acetate - allylidene diacetate, importance for the production of copolymers 70 vinylene carbonate - vinyl methyl ether, vinylene carbonate -

5 6

Monovinylacetylene, vinylene carbonate - methyl methacrylic acid and anhydride, esters such as methyl propionate, acetals,

lat, vinylene carbonate — monovinylacetylene — methyl meth- such as dioxolane, mercaptans, bisulfites or silicone halo-

acrylate, vinylene carbonate — methacrylic acid, vinylene car- genide, hydrochloric acid, etc.

bonat — ethylene glycol dimethacrylate. The polymerization or copolymerization can

Polymerizable compounds that have a majority of 5, optionally without the addition of a special catalyst

Have ethylene double bonds and are made with vinylene carbonate, but in general it is useful to have one

can be copolymerized at high pressures, use a catalyst to achieve a high reaction

include those that allow conjugated double bonds to achieve speed. There are peroxide

have e.g. B. butadiene, 2-chlorobutadiene, 2-fluorobutadiene, and azo catalysts in question. The catalysts

2-Phenoxybutadien and isoprene, and compounds which can be inorganic or organic ^10; the latter

two or more isolated ethylene double bonds have the general formula R'OOR ", in which R 'is a

hold, e.g. B. methacrylic anhydride, acrylic acid ester organic radical and R "an organic radical or

and substituted acrylic acid esters of polyhydric alcohols. Is hydrogen. These connections become general

Compounds with a conjugate with a carboxyl group are called peroxides, and are specifically hydroper-

Gated ethylene groups include diallyl maleate, vinyl i5 oxides, when R "is hydrogen. R 'and R" can

methacrylate, allyl methacrylate, crotyl methacrylate, meth- hydrocarbon radicals or organic radicals,

allyl methacrylate and compounds which are not conjugate with a large number of substituents

gation of the polymerizable ethylene groups with Carb- can be tuiert. Examples of suitable peroxide catalysts

have oxyl groups, including diallyl phthalate, dispersants are: benzoyl peroxide, tertiary butyl peroxide,

allyl carbonate, diallyl adipate, diallyl fumarate, divinyl a ° tertiary butyl hydroperoxide, diacetyl peroxide, diethyl

succinate, divinyl adipate, and divinylbenzene. peroxydcarbonate, dimethylphenylhydroperoxide (also

While mostly compounds that have a terminal methyl known as cumene hydroperoxide), hydrogen peroxide, have lengruppe, as mixed monomers with vinylene potassium persulfate, perborate and other inorganic percarbonate fumaric acid compounds can also be preferred. The azo catalysts are and maleic acid derivatives can be used. Thus, 25 entities of the group —-N = N —- in the molecule can characterize maleic anhydride and dialkyl esters of fumaric acid; the free valences can be transferred to numerous and maleic acid such as B. Diethyl and Dimethylfumaiat niche radicals be bound, however, a pre- and maleate, is preferably bonded to a tertiary carbon atom with vinylene carbonate by the process. are copolymerized according to the invention, and there are examples of suitable azo catalysts: α, α'-Αζο-can Interpolymers or mixed polymers of them 30 diisobutyronitrile, diazoaminobenzene, azobis (diphenyl the additional inclusion of other monomethane) and a.a'-azobis-a.y-dimethylvaleronitrile. the mers, such as B. ethylene, vinyl chloride or styrene, herge peroxide and azo catalysts are in low, but will be presented. Carbon monoxide, sulfur dioxide and catalytic amounts are used, which in general are not Acethylene are in the same way with vinylene carbonate over 1 weight percent, based on the monomer according to the method according to the invention, mixed-poly 35 mixture. A suitable amount is often in that merizable. Range from 0.001 to 0.5 weight percent.

There are also other classes of mixed monomers. The polymerization can also take place in the presence of

for copolymerization with vinylene carbonate in small but catalytic amounts of molecular

Question, and practically any material that can run with oxygen. Pure oxygen is

Vinylene carbonate react at high pressures and is particularly suitable. It is expediently 10 to 200 parts

polymeric molecule can form. Oxygen per 1 million parts of monomeric material,

The mixed monomers should preferably be used olefinically based on the weight,

be unsaturated and can contain 3 or more carbon-ethylenically unsaturated compounds

contain atoms per molecule. Mixed monomers that are not subjected to a pressure of at least 70 kg / cm ² below the inlet

contain more than 30 carbon atoms per molecule, 45 flux of ionizing radiation are from polymerizing inte-

generally particularly useful. be polymerized. A

In the case of copolymerization, 5 to 95 weight y radiation can be used, which is preferably from a radio-

percent vinylene carbonate and 5 to 50% of an active substance such as cobalt 60 is obtained. Press

Several other unsaturated organic, thus mixed, of at least 1400 kg / cm ² are particularly preferred,

polymerizable compounds (based on the 50 The reaction time depends, among other things, on the

total weight of the monomers) are used, the desired percentage conversion. It can

if necessary, however, there are also quantities of one of the grain-high conversions which are 100% of the mono-

components up to 1 percent by weight or less are available. closer to being achieved. However, it may be desired

According to the invention can also be modified poly- to limit the conversion to a value

more products are obtained, known as telomeres 55 which are significantly less than 50 percent by weight of the

and by carrying out the polymerization it is brought into consideration by monomeric material, e.g. 10 to 30%

wart can be obtained from substances undergoing the polymeric conversion. Unconverted monomers can

sation conditions are not polymerizable, recovered from the reaction mixture and given

however, with a number of units of the monomers, if necessary after purification, they can be returned to the polymerization.

unite. The products that are passed through such a telomeric 60.

cation or chain rearrangement reaction are obtained, The reaction time depends on numerous factors,

can be represented by the formula Y (A) _n Z, in particular the pressure, the type and amount of catalyst

the A is a divalent radical and vinylene carbonate sators, the purity and the proportions of the monomers

or this and other monomers, if one and the presence of any additional reaction

Mixed monomer is used, η an integer between 65 media. It also depends on the reaction

2 and 50 or above and Y and Z terminated on one are carried out continuously or discontinuously.

Chain of monomeric units are linked links, the reaction time can optionally be several days

which together amount to one molecule of the non-polymerizable, but mostly a reaction time that

Forming compounds, for example halogen compounds, does not exceed 24 hours, sufficient. At discount

such as carbon tetrachloride, acids such as isobulter- 70 continuous reactions usually occur

7 8

times from 1 to 20 hours are possible; with continuous addition to ethylene and vinylene carbonate can

Reactions, the reaction times are shorter and can still use other monomeric materials in the polymerization

be in the range of a few minutes to a few, e.g. B. vinyl chloride, vinyl acetate, vinyl

Hours, e.g. B. 1 minute to 5 hours. fluoride, propylene, styrene, acrylonitrile and other un-

The polymerization can take place in the presence of additional 5 saturated organic compounds.

Reaction media, e.g. B. gaseous or liquid carrier hydrogen can be used in the copolymerization

medic-n such as water or organic liquids, can be used to make a modified copolymer

leads to be; it can also be used to obtain such media from ethylene and vinylene carbonate. One

be that a Lcsur.gswirkung on the polymeric material suitable amount of hydrogen is z. B. 0.5 weight

have rial, e.g. B. acetone, benzene, xylene, cyclohexane, io percent of the monomeric material.

Hexane, dioxane, methyl ethyl ketone. The use for- The polymers obtainable according to the invention and additional reaction media is particularly important when copolymers can be used for the production of natural \ * experience of importance. Water can be injected or compression molded into objects Amounts of e.g. B. 0.5 to 5 parts by weight to be used on the mono. They can be made of fibers, threads mere material related, are used. When applying 15 or films are produced, whereby the products are given of water can be suspended in this and, if necessary, dissolved beforehand. Some ethylene or Emulsifiers are added. Vigorous stirring Vinylene carbonate copolymers are particularly suitable for it is advisable to carry out the polymerization, the production of films after the balloon inflation is particularly when using water. Suitable for liquid reac- tions.

tion media support the control of the temperature, ao the polymers obtainable according to the invention and

since the polymerization is strongly exothermic. If dissolving copolymers are used with other resins and poly-

or non-dissolving liquid organic reaction or meren substances well tolerated. They can be soft

The carrier medium to be used are usually makers, modifiers, fillers, stabilizers,

at least 1 to 5 or 10 parts by weight per 1 part by weight of pigments, etc. may be incorporated. According to the invention

monomeric material sufficient. The aim is to ensure that the products available can be solid, semi-solid or

be that the exothermic heat of reaction is removed and liquid according to the choice of polymerization

thus an excessive rise in temperature during the components and the way in which the process is carried out

Polymerization is avoided. be.

Under suitable conditions, monomeric vinyls can be used.

lencarbonate units in the polymeric material a 3 ° standing explained in more detail.
Undergo hydrolysis leading to the presence of units

of the following type leads in the polymer: Example 1

The copolymerization of ethylene with vinylene

Yy 35 carbonate was released in a high pressure shake bomb.

■ led. This was with thermocouples for measurement

- C - C - provided the reaction temperature and through a high

pressure line connected to a water tank where-O O in the case of water for generating and regulating the pressure

4 ° was used on the reaction mixture.

jj jj 0.15 g was put into the bomb, which was surrounded by ice

α, α'-azodiisobutyronitrile as a catalyst and 20 g vinylene carbonate brought in. The bomb was closed

The extent of hydrolysis can, depending on the reaction, be cooled in dry ice (solid CO ₂ ) and then evacuated under conditions of a very low percentage 45 while it was at dry ice temperature. The evacuated bomb cooled of the vinylene carbonate units in the polymeric material would then range with pure to essentially complete hydrolysis. Ethylene (approximately 100 g) filled.

When the polymerization was completed in the presence of water, the bomb thus filled was placed in the shaker

is performed, one can expect that the hydrolysis will be brought in and the temperature on the automatic controller will occur to a limited extent, especially if the water is set to 55 ° C; the bomb has been used for 1 hour if the medium is acidic or alkaline. Simple polymeric left, taking it to the temperature of the regulator sation in the presence of water does not seem warmed in larger (shaker). Meanwhile, volume hydrolysis of vinylene carbonate monomers or the bomb was pressurized by means of vinylene carbonate units in the polymer to effect 350 kg / cm ² , after which the compound became the ken. Of course, the hydrolysis is all the more extensive the more 55 water tanks are closed. The pressure at which the reaction time is longer. It may be desirable, a bomb changed his height when the bomb reached 55 ⁰ C hydrolysis of Vinylencarbonateinheiten in the poly-, the temperature was then raised to 75 ° C, mers to obtain. The presence of hydroxyl groups After 45 minutes the pressure rose to 1550 kg / cm ² and in the polymer allowing further reactions with then fell rapidly to 840 kg / cm ⁸ ; at this point began various reagents, e.g. B. aldehydes to generate the pressure to change its level. Acetals were generated from the bomb and unreacted material was drained off the polymer. When opening the sensitivity and often stickiness. In a homo bomb, 30 g of a white sponge-like polymer were found and where the percentage of vinylene copolymer of ethylene and vinylene carbonate carbonate in a copolymer is sufficiently high, an analysis of the copolymer obtained

a water-soluble polymer can be produced by hydrolysis 65 that its oxygen content is 6 percent by weight. The same hydrolysis amounts, corresponding to 10.7 percent by weight of vinylene methods in the homopolymers described here, can be carbonate units in the copolymer,
and copolymers are used, as in the The properties of the copolymers were after

Hydrolysis of vinyl acetate polymers determined for the BiI standard plastic test method. In the Generation of polyvinyl alcohols can be used. 70 Table I below are the values thus obtained in

I 040 789

Tabular form together with typical values for one of the best commercially available polyethylene.

Certain test methods, such as for density, solubility, etc., are readily apparent. Others used Methods were the following:

I. Copper rod thermal properties

A. Softening temperature.

B. Melting temperature.

The test was carried out with a copper rod heated at one end and cooled at the other, so that in this way a surface was formed, the temperature of which varies along the rod between them Extremes changed. Thermometers were placed in the rod in gaps to show the temperature to determine the individual parts. Particles of the polymer to be tested were longitudinally in a thin layer sprinkled on the pole. After 10 minutes the following observations were made.

Softening point: This was determined by brushing the sample with a bristle of a soft brush. The lowest temperature at which the sample just began to stick to the bar was used as the softening point fixed.

Melting point: The lowest temperature at which the particles began to lose their shape was set as the melting point.

II. Melt index number

A. Injection speed, milligrams per second.

B. Elastic aftereffect in%.

A cylindrical steel chamber was kept at 190 ° C. An opening 1.6 mm in diameter and approximately 15 mm in length was drilled into the bottom of the cylinder. A steel stamp with a weight on top was used to develop the injection pressure on the polymer. The sample to be tested was first Rolled for 5 minutes and then diced to obtain a uniform product free from Gas was injected. After the cube-shaped particles were introduced into the spray chamber and the The stamp was placed on the polymer 5 Mi-

^X 5 minutes allowed to reach temperature equilibrium with the chamber. The weight was then placed on the stamp, and. the splash started. The spray strand was cut at the opening, a timer was started and the strand was then cut several times. The strand sections were weighed and the injection speed determined in milligrams per second. The determination of elasticity involved measuring with a micrometer the diameter of the extruded strand at the end that was extruded first. The percentage recovery or elastic aftereffect was calculated as follows:

percentage recovery =

measured diameter - opening diameter

Opening diameter

X 100.

III. Parallel plate plastometer values

A. Viscosity in PoisenXl0 ~ ^e .

B. Molecular weight (mean weight).

The Tinius-Olsen ParaUel-plate plastometer was used at used for this purpose. Essentially, this consists of a system through which a constant force is applied to two parallel plates, which are kept at a constant temperature and between one shaped disc is brought from the plastic to be tested. The thickness changes are at time intervals of the test body measured. Through this test, the flow of the plastic material is under the applied stress measured at elevated temperatures, giving a melt viscosity number , from which the average molecular weight can approximately be calculated.

IV. Module properties (Clasb-Berg)

A. Brittleness temperature (T _f in ⁰ C).

B. rubberiness temperature (! T ₂₀₀₀ in ⁰ C).

This test is a measurement of the slope of a plastic sample as a function of temperature, measured by means of a torsion test. The approach is essentially that described by Clash and Berg, Industrial and Engineering Chemistry, 34, p. 1218 (1942). The brittleness temperature (T _f ) is the temperature at which the stiffness modulus is 135,000 (9500 kg / cm ² ). The rubberiness temperature (T _mo ) is the temperature at which the modulus of stiffness has a value of 2000.

X. Loading properties

45

A. Strength to flow in kg / cm ² .

B. Breaking strength in kg / cm ² .

C. Elongation to flow in%.

D. Elongation at break in%.

These tests were determined according to the standard tests So ASTM D 638-46 T, D 412-41.
The comparison values are as follows:

Table I.

Comparison of the physical properties of ethylene-vinylene carbonate copolymer with those of

commercial polyethylene

Physical Properties Commercially available
Polyethylene Ethylene vinylene carbonate
Mixed polymer I. Copper rod thermal properties
A. Softening temperature in ⁰ C ..............
B. Melting temperature in ° C. ■
II. Melt index number
A. Injection speed in mg / sec
B. elastic aftereffect in%
III. Parallel plate plastometer values
A. Viscosity in poises χ 10 ~ ^β
B. Molecular weight (mean) 102
125
2 to 4
50 to 60
0.5 to 1.5
20,000 105
120
7.7
53
0.52
19,000

809 657/492

continuation

Table I.

Physical Properties

Commercially available
Polyethylene

Ethylene vinylene carbonate
Mixed polymer

IV. Module properties (Clash-Berg)

A. Brittleness temperature T _f in ° C ....

B. rubberiness temperature _{T 2000} in ^{0 C.}

V. Solution viscosity

A. Specific viscosity 0.1% in xylene at 99 ° C

VI. Solubility in organic solvents

A. cold (25 ⁰ C) .....

B. hot (8O ⁰ C)

VII. Density

A. Density at 25 ° C in g / ccm

VIII. Clarity

A. Visual inspection of the fitting

IX. Surface gloss

A. Visual inspection of the fitting

X. Loading properties

A. Strength to flow in kg / cm ²

B. Breaking strength in kg / cm ²

C. Yield elongation in ° / ₀

D. Elongation at break in%

-32.0
85.0

0.08

insoluble

soluble in xylene,

Carbon tetrachloride

0.917

very cloudy and
opaque

semi-matt and a little rough

84 to 98
126 to 140

50
450 to 500

-32.8
82.3

0.07

insoluble

soluble in xylene,

Carbon tetrachloride

0.959

weakly cloudy

shiny and smooth

96
156

80
470

: The above values show that the copolymer is generally comparable to commercial polyethylene in most respects and certain has important improvements over this. Ethylene-vinylene carbonate copolymer is much clearer than polyethylene. It has a better surface gloss. In addition, the ethylene-vinylene carbonate copolymer was used very stable to processing treatment, d. H. it showed no evidence of thermal degradation. The rolled material had and had good flow as measured by the ejection speed low elastic aftereffect. This is in the same range as the special technical polyethylene, that is described in Table I, and this value is much lower than that for many other engineering polyethylenes. A low elastic aftereffect is, of course, particularly with the end use "of the polymer" when spraying, desirable. In terms of loading properties, the percentage elongation was up to to give better than that of the commercial polyethylene, as is also the case with the breaking strength of the Case was.

The above comparison has been made on the basis of commercially available polyethylene. An important Feature of the invention results from the consideration of the fact that, if under the same reaction conditions as for the preparation of the ethylene-vinylene carbonate copolymer of this example were used, ethylene is polymerized alone, a cross-linked, cross-linked polyethylene product is obtained, which is not processed in a technical plant as it is commonly used for processing polyethylene.

Example 2

In the high pressure polymerizer described in Example 1 vinylene carbonate and ethylene were copolymerized in the manner indicated in Example 1. The cooled bomb was with 20 g of vinylene carbonate and 0.15 g of α, α'-azodiisobutyronitrile catalyst loaded. The bomb was closed, chilled in dry ice, evacuated, and then with pure ethylene (approximately 100 g) filled.

The loaded bomb was placed in a shaker and immediately pressurized to 350 kg / cm ² . Once the temperature reached 50 ° C, the pressure had risen ^{to approximately 1050 kg / cm 2.} The pressure was then adjusted ^{to 1400 kg / cm 2} with an automatic regulator for 17 hours.

There were 6 g of a somewhat yellowish ethylene-vinylene carbonate copolymer won.

Example 3

A copolymer of vinylene carbonate with styrene was prepared from 80 g of styrene and 20 g of vinylene carbonate without the addition of a polymerization catalyst by placing the starting material in a high pressure bomb and _{cooling the bomb in dry ice (solid CO 2} ). She was then evacuated and heated to 120 ⁰ C. The bomb was pressurized with water to 350 kg / cm ² and the pressure was gradually increased at half-hour intervals. The temperature was finally ^{brought to 190 °} C. for a short time in order to obtain the most complete possible polymerization.

The product obtained was a solid, transparent and colorless material suitable for molding, injection molding and pouring, e.g. B. for the production of a clear film is suitable. If one works at the temperature conditions mentioned, it can happen that part of the polymer is converted into a darker decomposition product. If one does not wish to obtain dark products, it is advisable to work under milder temperature conditions, e.g. B. at 90 ⁰ C and a pressure of 1400 kg / cm ² or at 80 ⁰ C and a pressure of

2800kg / cm ² . ■ · '"■■""■"■' ^ - '-S''-

Example 4

In the manner explained in Example 1, vinylene carbonate and vinyl chloride were copolymerized in the high pressure polymerizer. The reaction bomb was charged with 125 g of vinyl chloride, 20 g of vinylene carbonate and 0.03 g of benzoyl peroxide as a catalyst. The bomb was pressurized with water to 1750 kg / cm ² and kept at a reaction temperature of 75 ° C. for 16 hours. The formation of 132 g of a high molecular weight vinyl chloride-vinylene carbonate polymer resulted. This material was formed into a clear, rigid, but pliable (not brittle) sheet.

Examples 5 to 10

Each of the following interpolymerizations was carried out by enclosing 6 to 7 mg of benzoyl peroxide plus the stated amounts of vinylene carbonate and comonomer in a compressible steel tube. The sealed tubes were then placed in the pressure bomb and subjected to a pressure of 1750 kg / cm ² at an internal temperature of 70 ° C. for 20 hours. The tubes collapsed so that the internal pressure was equal to the external pressure. But they remained locked. After the completion of the polymerization, the tubes were opened and the polymer was then obtained therefrom.

Table II

example Vinylene
carbonate
ing Comonomer lot
ing yield Mixed polymer
nature 5 1.2 Acrylonitrile 4.8 essentially
Completely clear, hard, quite elastic 6th 0.6 Styrene 5.4 essentially
Completely crystal clear, stretchy 7th 0.6 Vinyl acetate 5.4 Completely crystal clear, hard, but elastic 8th 1.2 Vinyl acetate 4.8 Completely crystal clear, softer and more stretchy
as an example 7 9 0.6 Methyl methacrylate 5.4 Completely crystal clear, strong finishes
shiny, hard, but elastic 10 1.2 Methyl methacrylate 4.8 Completely clear, less similar appearance,
less uniform film, stretch
cheaper than example 9

Example 11

In accordance with the procedure in Example 4, the bomb was charged with 95 g of vinyl fluoride, 5 g of vinylene carbonate and 0.05 g of α, α'-azodiisobutyronitrile as catalyst and placed under a pressure of 1190 kg / cm ² . A temperature of 75 ° C. was maintained for 3 hours. The yield was 25 g of a clear, hard copolymer of vinyl fluoride and vinylene carbonate.

Claims (7)

Claims: 40 45 1. A process for the preparation of polymers and copolymers, characterized in that vinylene carbonate is subjected to polymerizing conditions ^{under high pressure of at least 350 kg / cm 2.} 2. The method according to claim 1, characterized in that the polymerization is carried out under a pressure of at least 1050 kg / cm ² . 3. The method according to claim 1 or 2, characterized in that the polymerization is carried out under a pressure between 1400 and 2800 kg / cm ² and at temperatures between 35 and 125 ° C. 4. The method according to any one of claims 1 to 3, characterized in that vinylene carbonate together with at least one other unsaturated organic compound copolymerizable with it, including those with the y C = C ^ group, such as ethylene, styrene, acrylonitrile, acrylyl and Alkacrylylverbindungen and other vinyl and vinylidene compounds is polymerized. 5. The method according to any one of claims 1 to 4, characterized in that a vinylene carbonate is used is that by chlorination of ethylene carbonate to monochlorethylene carbonate and subsequent Dehydrochlorination of the monochlorethylene carbonate produced by reaction with an amine has been. 6. The method according to claim 1, characterized in that a mixture of ethylene and vinylene carbonate is subjected to copolymerization at a pressure of at least 350 kg / cm ² and at least part of the vinylene carbonate units in the resulting polymeric material is hydrolyzed to hydroxyl-containing units. 7. The method according to any one of claims 1 to 4, characterized in that a monomeric material with 95 to 70 parts by weight of ethylene and 5 to 30 parts by weight of vinylene carbonate is subjected to copolymerization at a pressure of at least 350 kg / cm ² to form a usually solid polyethylene-like To produce material. © 809 657/492 9.5 *