DE1570478A1 - Process for the polymerization of vinylaryl compounds with tert-butyl peroxyisopropyl carbonate and benzoyl peroxide - Google Patents

Description

Dlpl.lno.-F. "

Patent Attorneys I Or Exile! I Ί R 7 Π Δ-7 Ω

8th ;:

THE DOW CHEMICAL COMPANY, Midland, Michigan / USA

Process for the polymerization of vinylary compounds

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with terto-butyl peroxyisopropyl carbonate and benzoyl peroxide

The present invention relates to a method of polymerization of Vinylary! compounds and especially a new one Catalyst combination for the production of vinylaryl polymers.

It is known to use vinyl aryl polymers such as polystyrene or copolymers of styrene with other ethylenically unsaturated Monomers, by heating the monomers in bulk, in emulsion or in aqueous suspension without or in a mixture with to produce a polymerization initiator or catalyst or a combination of catalysts »

It has been proposed to use styrene in contact with an initiator or to polymerize a catalyst made from dicumyl peroxide or a mixture of benzoyl peroxide and di- (tert-butyl) peroxide or tert-butyl perbenzoate. It has also been suggested

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Vlnylarylverbindungen diperphthalate di-tert-using a mixture of benzoyl peroxide and a, a mixture of 2,2-D1- (tert-butylperoxy) butane and benzoyl peroxide or a mixture of tert-butyl perbenzoate and benzoyl peroxide as an initiator _o or catalyst to polymerize. Furthermore, it has been proposed, vinyl aromatic compounds by using a mixture of di-tert-butyl peroxide and Terto-butyl perbenzoate or a mixture of di-tert, -butylperoxyd and tert-Butylperaoetat as a catalyst to polymerize, and further styrene with rubber using a two catalyst system to polymerize, which consists of terto-butyl perbenzoate and an azo catalyst »

The object of the present invention is to provide one advantageous process for the polymerization of vinylaryl compounds and a new catalyst combination for this »

It has now been found that vinylary compounds in contact with a catalyst composed of both a benzoyl peroxide and terto-butyl peroxyisopropyl carbonate can be readily polymerized to form normally solid resinous thermoplastic polymers with improved flow properties, Surprisingly, it has been found that styrene polymers by Initiation of the polymerization reaction with a catalyst consisting of benzoyl peroxide and tert-butyl peroxydisopropyl carbonate (^ are produced, similar solution viscosity properties

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th within a given narrow range while simultaneously changing the melt viscosity of the polymer by changing the proportions of the cocatalyst materials used in the polymerization, among otherwise similar ones Reaction conditions in terms of time and temperature can be easily effected

The cocatalyst material can be a mixture of terto-butyl peroxyisopropyl carbonate and benzoyl peroxide or a derivative of benzoyl peroxide with one or more halogen atoms, such as chlorine, bromine or fluorine, or one or more alkoxy or alkyl groups with 1 to 4 carbon atoms, such as mathoxy, ethoxy. , Propoxy and eutoxy, methyl, ethyl, propyl and butyl, bound to the aromatic nucleus, its "Suitable benzoyl peroxides are, for example, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromobenzoyl peroxide, fluorobenzoyl peroxide, methylbenzoyl peroxide, butylbenzoyl peroxide and butylbenzoyl peroxide, butylbenzoyl peroxide, benzoyl peroxide. The cocatalyst materials can be used in amounts, the O ₅ 02 to 1.0 and preferably 0.05 to 0.5 parts by weight of fererto-butyl peroxydisopropyl carbonate and 0.02 to 1.0 parts by weight of benzoyl peroxide or a halogen> alkoxy or Alky! Derivative of this 100 parts by weight of the polymerizable monomers used at the beginning correspond _o

The vinylaryl compounds that react with the cocatalysts to form the polymeric products with the improved liquid properties

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Shafts can be polymerized.sind monoviny! aromatic compounds and ring-substituted monoviny! aromatic compounds of the general formula CgH, RR * -CH = CH ₂ , in which R and R ⁹ each have a hydrogen or halogen atom or an alkyl radical with 1 to 4 carbon atoms mean. Homopolymers and copolymers of two or more such monovinylaromatic compounds can easily be prepared using the cocatalysts defined here, as can styrene polymers containing at least 50% by weight of at least one such monovinylaromatic compound and up to 50% by weight of another monoethylenically unsaturated one Monomers which can be copolymerized with it, such as, for example, methyl methacrylate, vinyl acetate, vinyl propionate, α-methylstyrene or acrylonitrile

The polymerization of the monomers can be in bulk., In emulsion or in suspension at temperatures between about 80 and 150 ^e C and at atmospheric, subatmospheric or Uberatinosphärischem pressure performed.

The polymerization reaction can be carried out while the monomers are mixed with a volatile organic Liquid, as defined below, which is soluble in the polymer but does not dissolve the polymer, are present, to form an expandable polymer that can be foamed into a cell mass when heated. With an alternative Procedure, the polymerization can be carried out in aqueous suspension using the cocatalysts, suitable

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neterweise, to about 25 to 50 Gevi .-% of the monomer are polymerized, after which a volatile liquid organic foaming agent, such as an aliphatic hydrocarbon or an aliphatic halogenated hydrocarbon, which ^{boils below iiO e} C, to the polymerization mixture, preferably in about 2 to 15% by weight of the amount corresponding to the monomers used at the beginning, is added before more than about 80% by weight of the monomer have polymerized, after which the polymerization is terminated to obtain polymer grains or granules which contain the blowing agent in a uniformly distributed manner.

Another procedure for making foamable styrene polymer beads is to put the monomer in an aqueous suspension with a suspending agent such as Methyloellulose, sodium carboxymethyl methy! Cellulose, tricalcium phosphate, Magnesium carbonate, zinc oxide or hydroxyapatite, is stabilized to polymerize in a mixture with the cocatalysts, to obtain the polymer in the form of beads or granules, and then the polymer beads with a volatile organic liquid propellants such as pentane, petroleum ether or trichlorofluoromethane in the aqueous medium or the aqueous suspension in which the polymer is produced was to impregnate and then to recover the foamable polymer particles from the liquid.

The following examples illustrate the invention without restricting it.

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example 1

A charge of 100 g of styrene was placed in a 350 ml pressure-resistant glass bottle containing 150 g of deionized water and 3 g of zinc oxide. A charge of 0.5 g of benzoyl peroxide and 0.20 g of tert-butyl peroxyl isopropyl carbonate was added as a catalyst. The bottle was closed. The bottle was turned overhead in a liquid bath and heated to polymerize the monomer under the following time and temperature conditions: 7 hours at 90 * 0 and 5 hours at 115 ° C. The bottle was then cooled and opened. The polymer was filtered off, washed with dilute hydrochloric acid and then with water and dried. The product was in the form of discrete free flowing pearls. Fractions of the polymer were used to determine the solution viscosity and melt viscosity of the polymer. The solution viscosity was determined as the absolute viscosity in oP for a 10% strength by weight solution of the polymer in toluene at 25 ° C. The method for determining the melt viscosity corresponded to that of the publication "The Caplastometer, A New Melt Viscometer" by HJKaram et al. In Modern Plastics, Volume 32, Number 7 » page 129 (Mar. 1955) using an orifice 0.1 cm (0.040 inohm) diameter by 1.27 cm (0.5 inch) length with a nitrogen gas pressure of 700,000 dynes / cm (0.69 at) and a temperature of 227 * C. The tent for extruding a rod of the polymer 2.54 om (1 inch) in length under the specified conditions was measured. From the observed

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Measurements were made to calculate the Sohmelzviszosze in P. That The polymer had a solution viscosity of 12 cP and a solubility viscosity of 412 P. It contained << 0.05 # volatile constituents.

For comparison purposes, styrene was polymerized under appropriate conditions with the exception that only 0.5 g of benzoyl peroxide was used as the catalyst. This polymer was found to have a solution viscosity of 12.8 cP and a melt viscosity of 792P. It contained 0.25 % volatiles.

Example 2

Styrene was polymerized by a procedure similar to that of Example 1, using 0.15 g of benzoyl peroxide and 0.50 g tert-butyl peroxyisopropyl carbonate were used as a catalyst per 100 g of styrene monomer. The polymer had a solution viscosity of 24.4 cP and a melt viscosity of 1,120 P.

In contrast, it was found that under appropriate conditions, but using only 0.50 g of tert-butyl peroxyisopropyl carbonate as a catalyst, polymerized styrene resulted in a polymer having a solution viscosity of 25.5 cP and had a melt viscosity of 2210 P »

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Example 3

In each of a series of experiments, a charge of 100 g of styrene in an aqueous suspension of 150 ml of water containing 3 g of zinc oxide as a suspending agent and using both benzoyl peroxide and tert-butyl peroxyisopropyl carbonate was made in the table given in the table below Quantities polymerized as a catalyst. The polymerization conditions were 7 hours at 90 ° C. and 5 hours at 115 ^° C.

Table I shows the experiments and the proportions of catalyst materials used in carrying out the polymerizations. The table also shows the solution viscosity and melt viscosity determined for the polymer.

Table I.

Source materials Benzoyl
peroxide
weight tert-butyl
peroxy! sopro-
pyl carbonate
weight polymer Melting
Viscose
kind P fleeting
Duration
share £ attempt Styrene
weight 0.03 0.20 Solution
viscous
type c P 8811 0.05 1 100 0.10 0.20 40.6 5178 0.05 2 100 0.15 0.20 38.8 2011 0.05 3 100 0.15 0.03 39.8 7818 0.82 4th 100 0.15 0.10 42.9 5943 0.08 5 100 0.15 0.15 41.8 3426 0.05 6th 100 41.7

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Example 4

A charge of 100 g of styrene, in which 0.2 g of p-chlorobenzoyl peroxide and 0.2 g of tert-butyl peroxyisopropyl carbonate were dissolved, was dissolved in an aqueous suspension of 150 ml of water containing 3 S basic magnesium carbonate as a dispersant by agitation and Heating the suspension under the following time and temperature polymerization conditions polymerizes 7 hours at 90 ^° C and 5 hours at 115 ° C. The product was obtained as free-flowing discrete particles of polystyrene with improved flow properties, as determined by its melt viscosity properties, compared to polystyrene produced with each of the cocatalysts alone under otherwise identical polymerization conditions.

Example 5

A charge of 100 g of styrene in which 0.2 g of 2,4-dichlorobenzoyl peroxide and 0.2 g of tert-butyl peroxyisopropyl carbonate were dissolved as cocatalyst, was ic an aqueous suspension using a procedure similar to that used in Example 4 corresponded, polymerized. The polystyrene was obtained as a polymer with improved flow properties.

Example 6

A charge of TOO g of a mixture of about £? Wt .- $

Ra-vinyltoluene and 33% by weight p-vinyltoluene containing 0.2 g of benzoyl peroxide and 0.2 g of tert-butyl peroxyisopropyl carbonate as a cocatalyst as dissolved therein were polymerized in aqueous suspension using a method similar to that in Example 4 applied. The polymer was obtained as a product with improved puff properties _a

Example 7 .

A charge of 100 g o ~ vinyl toluene was in aqueous Suspension using 0.2 g of benzoyl peroxide and 0.2 g of tert-butyl peroxyisopropyl carbonate as cocatalyst after a Polymerized procedure similar to that used in Example 4. The product was obtained as a polymer with high heat resistance and good puff properties.

Example 8

A charge of 100 g of vinyl xylene in which 0.2 g of benzoyl peroxide and 0.2 g of tertiary butyl peroxyl isopropyl carbonate were dissolved as cocatalyst was polymerized in aqueous emulsion by a method similar to that used in Example 4. The polymer was obtained as a granular product with good pilling properties.

Beiaplel 9

A charge of 100 g of a mixture of 50 wt. ^

and 50 wt .- # methyl methacrylate, in which 0.2 g benzoyl peroxide and 0.2 g of tert-butyl peroxyisopropyl carbonate were dissolved polymerized in aqueous emulsion by a method similar to that used in Example 4. The product was sold as a granular copolymer obtained with good flow properties.

Example 10

A charge of 100 g of p-tert-butylstyrene in which 0.2 g Benzoyl peroxide and 0.2 g of tert-butyl peroxyisopropyl carbonate were dissolved, was polymerized in an aqueous emulsion by a method similar to that used in Example 4. The product had good flow properties.

Example 11

A charge of 100 g of a mixture of 75 parts by weight styrene and 25 percent by Ji -.% A-methylstyrene was polymerized in aqueous emulsion using 0.2 g of benzoyl peroxide and 0.2 g of tert-butylperoxyisopropyl carbonate as a cocatalyst for a method which corresponded to that used in Example 4. The product was a copolymer with good flow properties "

Example 12

A charge of 100 g of a mixture of 70 wt % styrene and 50 wt% acrylonitrile wherein 0.2 g benzoyl peroxide and 0.2 g

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tert-Butylperoxyisopropylcarbonat were dissolved, was in aqueous emulsion polymerized by a method similar to that used in Example 4. The product was a Copolymer with good flow properties.

Example 13

A charge of 100 grams of a mixture of 85 wt% styrene and 15 wt .- # vinyl propionate containing 0.2 g of benzoyl peroxide and 0.2 g of tert-butyl peroxyisopropyl carbonate was polymerized in aqueous emulsion by a method similar to the used in Example 4. The product was a copolymer with good flow properties.

Example 14

A charge of 100 g of a mixture of 80 wt -.% Isopropyl and 20 wt .- # p-tert-butylstyrene was by aqueous emulsion using 0.2 g of benzoyl peroxide and 0.2 g of tert-butylperoxyisopropyl carbonate as a cocatalyst, polymerized using a procedure similar to that used in Example 4. The product was a copolymer with good flow properties.

Example 15

A load of

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100 g of styrene in a 350 ml glass bottle in suspension in one aqueous medium of 150 ml of water with a content of 2 g of hydroxyapatite (experiments 1 and 2 in Table II) and 0.18 g of sodium polyvinyltoluenesulfonate and 0.57 g of ammonium sulfate (Experiment 3 in Table II) polymerized as a dispersant. As a cocatalyst was a mixture of benzoyl peroxide and tert-butyl peroxyisopropyl carbonate used in the amounts given in the table below.

The polymerization was carried out in a sealed bottle by turning it upside down in a liquid bath under the following time and temperature conditions: 3 hours at 80 ^° C, 6 hours at 90 ° C and 4 hours at 130 ° C. The polymer was then separated, washed, dried and tested using a procedure similar to that used in Example 1. Table II shows the experiments and gives the proportions of cocatalyst used when they were carried out.

Table II

Raw materials Benzoyl
peroxide
S. tert-butyl
peroxyisopro-
pyl carbonate
R. polymer Melting »
viscosity
P. attempt Styrene
G 0.05
0.15
0.20 0.15
0.15
0.15 Solution
viscosity
cP 3660
2880 1
2
3 100
100
100 25.1
26.9
25.1

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Example 16

A charge of 10Og styrene was added together with 0.25 g of benzoyl peroxide and 0.15 g of tert-butyl peroxyisopropyl carbonate as cocatalyst and 7.5 g of n-pentane as propellant in an aqueous suspension of 150 ml of water containing OtOk g of sodium polyvinyltoluene sulfonate and 0.16 g of ammonium sulfate polymerized by a procedure similar to that used in Example 15. The polymer was obtained as free flowing expandable beads. When heated with steam, the pearls expanded to 40 times the volume of the original volume of the pearls.

Example 17

A charge of 27 kg (60 pounds) of styrene, 41 g of benzoyl peroxide, and 41 g of t-butyl peroxyisopropyl carbonate was placed in a 76 l (20 gallon) steel reaction vessel lined with glass and equipped with a stirrer and heating and cooling devices, and 34 75 pounds of deionized water and 2 pounds of zinc oxide dispersant. The vessel was closed. The mixture was heated with stirring in the closed vessel at 90 ° C. for 7 hours and then at 115 ° C. for 5 hours. The polymer was obtained as free flowing beads containing 0.05 % monomer as determined by analysis of a test portion of the product. The suspension of the polystyrene beads in the reaction vessel was cooled to 95 ° C. Then a solution of 625 g

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157047 - 15 -

(1.38 pounds) bis (bromopropyl) bromopropyl phosphonate of the empirical formula

o = p

"509 S (0.24 pounds) of dicumyl peroxide and 2.45 kg (5.4 pounds) of η-pentane were added over 2.5 hours while continuing to stir and maintaining the mixture at a temperature of 95 ° C. After the addition of the solution, the resulting mixture was heated with stirring for a further 12 hours, the vessel was cooled to 30 ° C. and then opened, and dilute hydrochloric acid was added until the pH of the aqueous liquid was 2. The polymer was filtered off , washed with water and dried. PrUfanteile of the polystyrene were by heating with steam at 100 ^e C to a cell mass having a density of about 24 g / l (1.5 pounds per cubic foot) foamed. a sample of the foam was during ignition in open flame and subsequent removal of the flame self-extinguishing in 2 seconds «

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Claims (8)

Patent claims 1. A process for the polymerization of an a Vinylary! Compound-containing polymerizable liquid, characterized in that the polymer! Matable liquid is heated at a temperature between 80 and 150 ⁰ C in the presence of a Cokatalysatorkombination which consisting of a tert-butylperoxy isopropyl carbonate and a peroxide general formula in which R is a hydrogen »or a halogen atom or a Alkoxy or alkyl radical with 1 to 4 carbon atoms, alone or in combination. 2. The method according to claim 1, characterized in that benzoyl peroxide is used as the peroxide. 3 * method according to claim 1 or 2, characterized in that that styrene is used as the vinylary! compound. 4. The method according to any one of claims 1 to j $ *, characterized in that that the cocatalyst components in each case in amounts of 0.02 to 1 wt .- #. Based on the weight of the beginning polymerizable monomers used. 5. The method according to any one of claims 1 to 4, characterized 909828/1519 draws that the polymerization in a suspension polymeri ~ system is carried out. 6. The method according to claim 5 *, characterized in that the Suspension polymerization in the presence of a volatile organic Liquid that acts as a foaming agent when heated is able to work, is carried out. 7. The method according to claim 6, characterized in that η-pentane is used as the volatile organic liquid. 8. The method according to any one of claims 5 to 7, characterized in that an aqueous suspension stabilized with zinc oxide as the dispersant is used as the suspension. 9.0 9828/1519