DE1795395B2 - Process for the production of polymers and copolymers of (meth) acrylic acid ester or of acrylonitrile - Google Patents

Description

i 795 395

pressure of the gel effect can run, The by for the initial speed (F ₀ ) the at a

Attenuation of the gel effect initially a conditional increase in conversion from 0 to 10% achievable average value

the total polymerisation time can be represented by the Stei polymerisation rate.

delay the initial Polymerisationsgeschwin- speed (V _ma x), the Durchschnittspolymeri-

speed - be it by increasing the temperature or by sationgeschwiiidigkeit, which with a conversion of 60

by the type and amount of the used up to 80% is measured.

Initiator - balance. The first case occurs despite one.
this addition to be observed not a thermal shock. io In Experiment 1, methyl methacrylate was used in

It deserves to be emphasized that cyclic is known to contain 0.2 percent by weight of dilauroyl

Compounds having double bonds in or on the peroxide without the inventive additive at 6O ⁰ C

Ring, which in part has a similar structure as the polymerized. The value for Q is 32.

substances to be used according to the invention have, in experiments 2 to 5, increasing men-

a dampening of the Trommsdorff effect does not result in terpinolene, al ^ o an addition according to the invention

works. Of these ineffective rates within the meaning of the invention, also used, where O with increasing terpino

The same compounds are said to be methylenecyclohexane, and the quantities of lines decreased. As shown in curves 2 to 5,

monene, Λ-terpinene, l-ethylidene-cyclohexene-2, cyclo- this means that the addition of terpinolene increases

pentadiene and camphene as well as examples for increasing damping of the effect. The curves 4

Phatic compounds Geraniol, Pseudojonor, and 20 and 5 show a Poiymerisatiuüsverbindungen in which a

Farnesol mentioned by way of example. 1,3-Cyclohe ^ adiene ver gel effect no longer occurs.

Although the polymerization hesitates, it attenuates the gel

effect not. the polymerization of methyl methacrylate

In the following, numerical information is given under the influence of 0.2 percent by weight of

about the royl peroxide treated with the procedure according to the invention, one of the specialist

tied effect: the usual regulator, namely 0.3 "" Thioglycol-

With the use of the special compounds acid 2-ethylhexyl ester, also used. While without dampening or completely suppressing the addition of gel terpinolene Q has a value of 5.0, a reduction in the molecular weight is already effective, an addition of 0.01% terpinolene is associated with one of the polymers. This effect is, however, a decrease in this value, that is, as curve 7 shows so small that products of the same composition are shown, an, albeit slight, dampening of stinginess, which affects one with and the other without it. By increasing the number of connections according to the invention, the attenuation of the gel effect increases or the ecological behavior does not make a significant difference even with an addition of 0.05 weight. When the slight decrease in the molecular 35 percent disappears completely,
weight is undesirable, the associated on sheet 3 is the course according to experiment 4 the effect z. B compared by using small amounts according to experiment 11. At oem, the last to be compensated for in terms of crosslinking agents. - The cited experiment was an inventive method. On the other hand, the cited compounds were also not used at all. The resulting strong together with controllers, z. B. with mercaptans, the effective gel effect is determined by the high value for Q , with the effect regulating the molecular weight being pressed and demonstrated by the curve shape. The comparison of the two curves shows that, as the effect of the mercaptan is not described in experiment 4, the addition of. Terpinolene, the jolting effect that occurs with the gel

With particular advantage, the 45-like generation of heat according to the invention can be avoided and the

Process in bulk polymerization of Me polymerization nevertheless in practically the same time

methyl methacrylate is used, but it can be finished in such a way that either the initiation

The damping effect is also increased with the mixed polymer quantity or, as was the case in experiment 4

merization of (meth) acrylic acid esters and acrylic acid is, the polymerization temperature is increased

nitrile with z. B. styrene or vinyl acetate used 50 w'rd.

will. Azoisobutter was used in experiments 12 and 13

The in the table below and in the acid dinitrile used as initiator. Also in this

The experiments shown in the graphs show the case when an inventive device was also used

the effect achievable with the method according to the invention. Addition (1,4-cyclohexadiene) a practically complete

The monomer or the monomer mixture dampened the gel effect for 55 days.

under the action of an initiator in the dilatometer. In experiments 14 and 15, the polymerisation was

isötherm polymerized. The ratio of maximal- tion of methyl methacrylate under the one

speed and initial speed of each action of lauroyl peroxide once without and once

temporary course of polymerization is a measure of the addition according to the invention (l-methyl-l ^ -cyclo-

Damping effect, namely in the sense that a 60 hexadiene) carried out, with the result,

high value for the quotient that a gel effect in the procedure according to the invention did not occur, while without such an admission

O - ^{Vmax set> w} i ^e this shows the curve 14, the turnover between

V ₀ 20 and 95% in a short time under respectively

65 high heat generation was achieved.

the occurrence of a strong gel effect means that in experiments Io to 18, methacrylic acid

rend low values for this quotient a damping methyl ester and styrene in equal parts by weight and

mean fune of the gel effect. The value of the action of 0.5% lauroyl peroxide represents poly-

merized. While, as the quotient Q and curve 16 show, a strong gel effect occurred in the copolymerization without addition according to the invention, this was largely attenuated by the addition of 0.05 percent by weight of terpinolene; a lower addition of terpinolene (0.02%) already had a significant dampening effect on this effect.

Also in the polymerization of methyl acrylate and in the mixed polymerization of methyl acrylate together with methyl methacrylate (1: 1) the effect according to the invention occurred, such as this is clearly shown by the comparison of curves 19 and 21 on the one hand and curves 20 and 22 on the other hand.

The trial 23 was polymerized at the acrylonitrile under the effect of 0.1% Azoisobuttersäured.initril and at a temperature of 6O ⁰ C, could not be reproduced curve moderate; the

The polymerization was explosive. However, if 0.05 percent by weight of terpinolene is added to the monomer to, as shown by curve 24, the polymerization can be safely controlled.

Experiments 25 and 26 show the copolymerization of acrylonitrile with methyl methacrylate (1: 1). In this case, too, the addition of 0.05 percent by weight of terpinolene resulted in complete avoidance a gel effect.

The ίο shown in the curve 27 Experiment 27 the test is compared to 14 (polymerisation of methyl methacrylate under the action of lauroyl peroxide 0.2 weight percent at 50 ⁰ C). All other things being equal, 0.025 percent by weight of y-terpinene is dissolved in the monomer. This addition causes a complete avoidance of the gel effect.

attempt
Curve Monomer initiator According to the invention Tem
temperature
⁰ C Vmax_
V - ι / page 1 1
2
3
4th
5 Methacrylic acid methyl ester
Methacrylic acid methyl ester
Methacrylic acid methyl ester
Methacrylic acid methyl ester
Methacrylic acid methyl ester 0.2% lauroyl peroxide
0.2% lauroyl peroxide
0.2% lauroyl peroxide
0.2% lauroyl peroxide
0.2% lauroyl peroxide 0.01% terpinolene
<>, 02% terpinolene
0.05% terpinolene
0.1% terpinolene 60
60
60
60
60 32
8.5
2.6
0.92
0.5

attempt
Curve Monomer initiator Regulator additive Tem
temperature
⁰ C ν
^m
Q - κ. , approx 6th Methacrylic acid 0.2% 0.3% thioglycolic acid 60 5.0 methyl ester Lauroyl peroxide 2-ethylhexyl ester 7th Methacrylic acid 0.2% 0.3% thioglycolic acid 0.01% 60 4.0 methyl ester Lauroyl peroxide 2-ethylhexyl ester Terpinoles 8th Methacrylic acid 0.2% 0.3% thioglycolic acid 0.02% 60 2.6 methyl ester Lauroyl peroxide 2-ethylhexyl ester Terpinoles 9 Methacrylic acid 0.2% 0.3% thioglycolic acid 0.05% 60 0.76 methyl ester Lauroyl peroxide 2-ethylhexyl ester Terpinoles 10 Methacrylic acid 0.2% 0.3% thioglycolic acid 0.1% 60 0.48 methyl ester Lauroyl peroxide 2-ethylhexyl ester Terpinoles

attempt
Curve Monomer initiator Addition according to the invention Tem
temperature
⁰ C Q = - Max 4th Methacrylic acid methyl ester 0.2% lauroyl peroxide 0.05% terpinolene 60 0.92 S. 11th Methacrylic acid methyl ester 0.2% lauroyl peroxide 40 10.7, 12th Methacrylic acid methyl ester 0.1% 60 8.7 Azoisobutyric acid dinitrile W. 13th Methacrylic acid methyl ester 0.1% 0.05% 60 1.3 I. Azoisobutyric acid 1,4-cyclohexadiene ■ Ft dinitrile 14th Methacrylic acid methyl ester 0.2% lauroyl peroxide 50 18th 15th Methacrylic acid methyl ester 0.2% lauroyl peroxide 0.05% 50 1.33 > co l-methyl-l ^ cyclo- hexadiene 16 Methacrylic acid methyl ester 0.5% lauroyl peroxide 50 6.0 to styrene = 1: 1 17th Methacrylic acid methyl ester 0.5% lauroyl peroxide 0.02% terpinolene 50 3.4 Ξ to styrene = 1: 1 • s 18th Methacrylic acid methyl ester 0.5% lauroyl peroxide 0.05% terpinolene 50 1.1 to styrene = 1: 1

7th initiator 8th Tem
temperature
⁰ C 2.0 Max .siert attempt
Curve Monomer 0.1% Addition according to the invention 60 19th Acrylic acid methyl ester Azoisobutyric acid dinitrile 2.2 0.1% 60 S. 20th Acrylic acid methyl ester Azoi sobutyric acid M. . 5Γ to methacrylic acid methyl dinitrile 0.5 Oj
CO OO ester = 1: 1 0.1% 60 > Ä 21 Acrylic acid methyl ester Azoisobutyric acid 0.05% terpinolene dinitrile 0.7 60 S.
Sä * 22: Acrylic acid methyl ester dinitrile 0.05% terpinolene VO to methacrylic acid methyl ester = 1: 1 0.1% 60 explosive 23 Acrylonitrile Azoisobutyric acid good diiiitrile polymer 0.1% 60 1.7 24 Acrylonitrile Azoisobutyric acid 0.05% terpinolene dinitrile 0.1% 60 2.5 25th Acrylonitrile to methacrylic Azoisobutyric acid acid methyl ester = 1: 1 dinitrile 0.1% 60 0.64 26th Acrylonitrile to methacrylic Azoisobutyric acid 0.05% terpinolene acid methyl ester = 1: 1 dinitrile 0.2% lauroyl peroxyl 50 18 1 14th Methacrylic acid methyl ester 0.2% lauroyl peroxide 50 2.4 y 27 Methacrylic acid methyl ester 0.025% y-terpinene

For this purpose 3 sheets of drawings

Claims (1)

one by adding turpentine oil, rosin Claim: or lemon balm oil in the polymerization of (Metb -) - Acrylic acid esters, optionally together with acrylic Process for the production of polymers nitrile, styrene, butadiene or vinyl acetate (German Pavon Acrylic Acid Esters, Methacrylic Acid Esters !! or 5 tentschrift 632 951). In the USA process _1- Pa-acrylonitrile and more than 50 percent by weight of 1,942,531 vinyl esters or a mixed percentage of these monomers are mixtures of vinyl esters with styrene in the presence of polymerizates by polymerizing the monosolvents and small amounts of one terpene-like mers in bulk under the action of known substances, such as colophony, its derivatives, di-polymerization catalysts, thereby ge io pentene or camphor, polymerized in order to obtain low indicates that the polymerization in viscous polymers. The addition of soda-presence of compounds with a six-series is known from French patent 836 988 for ring, the two non-conjugated double bonds tier polymerization of ethylene. For those, one of which can be semicyclic, in order to achieve a significant dampening effect, not an amount of 0.005 to 0.1 percent by weight is carried out. so high that an undesirable softening effect occurs. In addition, the compounds used hitherto result in the polymerization of Styrene and methyl methacrylate show a distinct yellow 20 coloring of the polymer. In British Patent 1,026,145, the It is known that during the polymerization of certain production of low molecular weight copolymers, the monomers such. B. of (meth) acrylic acid esters, acrylic from maleic acid, maleic anhydride or a nitrile and styrene, in particular voa methacrylic acid half-ester of maleic acid (1 to 18 carbon atoms in the methyl ester, the polymerization rate after 25 alcohol residue) on the one hand and from at least one vinyl -Achieving a certain viscosity of the polymerizing or vinylidene compound are built up on the other hand, generating approach strongly. By increasing the described. The vinyl or vinylidene monomer viscosity of the action medium is the chain - is thereby gradually hindered to maleic acid, maleic acid termination. While the anhydride or male and a half ester is added to the gel formed, the monomers can still diffuse relatively unburned to the reaction under the action of a catalytic site, sine ⁴ the growing tor, ζ. B. a peroxide expires. To the strived for chains hindered in their movement. Since the aborted effect, namely the formation of low molecular weight copolymers normally in the unregulated polymerization, is achieved, regulators are used by adding two growing chains of the terpinolene type. These regulators must react with one another, if it is made more difficult by diffusion, as on page 2, lines 99 ff. And in the main claim, so that long chains arise. is given, in an amount of 0.5 to 30%, before the growth process continues at preferably 5 to 20%, based on the vinyl or practically constant rate, so that vinylidene monomers are used,
the gross speed increases. In the same way, the polymer of acrylic acid esters and methacrylic acid esters released per unit of time increases the heat of merization. In order to prevent excessive heating or acrylonitrile and more than 50 parts by weight of polymerizing material, which in turn would further increase the mixed poly initiator decomposition built up from these monomers and thus the polymerization merisates by polymerization of the monomers in speed, mass below the The action of known polymers must ensure that sufficient heat dissipation is achieved using catalysts which have a gel effect. This is then suppressed, especially in bulk polymerisation, without merisation acuie problem, in that a yellow coloration of the polymer or a favorable ratio of volume to upper side effect occurs when the polymerisation surface of the polymerising Shaped body, e.g. B. that in the presence of compounds with a six-plate or the block, is set by ringing in such a way that two non-conjugated double bonds polymerize correspondingly slowly or by the instructions, one of which can be semicyclic, in one The initial rate of the polymerization is carried out by a quantity of 0.005 to 0.1 percent by weight, suitable choice of accelerator and temperature. is kept low that the during the Gel- understands under a semicyclic double bond Dung occurring heat tone in sufficient 55 one such that leads from the ring into a side chain can be dissipated. Basically ("Textbook of Organic Chemistry" by Hans a constant rate of polymerization Beyer [1959], p. 452). Achieve compounds of the gekennzeichauch such that the polymerization are neten type, for. B. 1,4-cyclohexadiene, 1-methyl can begin at a relatively high temperature and the 1,4-cyclohexadiene, terpinolene, ß- and y-terpinene.
During the gel formation onset of increase in the 60 From the fact that, as already stated, the rate of polymerization by cooling granular terpinolene in greater, 0.5 to 30 percent by weight pens. In practice, this process can only be carried out to a limited extent in the polymerization to a limited extent. certain monomeric compounds as termination regulators It is already known that the addition of certain acts and thereby polymerizates of low mole substances gives rise to the gel or Trommsdorff effect of up to 65 kular weight, could not dampen the polymerization rate over, that terpinolene in very much smaller quantities to keep the entire sales range constant. The polymerization of acrylates, methacrylates or a certain damping of the Trommsdorff effect is achieved by acrylonitrile with damping or complete under-