CS196839B1 - Method for the radical polymerisation and/or copolymerisation of olefinically unsaturated monomers - Google Patents

Description

METHOD OF RADICAL POLYMERIZATION AND / OR COPOLYMERIZATION OF OLEFINICALLY UNSATED MONOMERS

According to the invention, it is possible to initiate polymerization and / or copolymerization of mainly vinyl monomers over wide temperature limits on the basis of readily available starting raw materials, to achieve sufficient reaction rates, uniformity of course and high molecular weight at lower than usual temperatures but still 1 ' technically and economically achievable even on conventional devices.

In order to prepare extremely high molecular weight polymers, polymerization of vinyl monomers, in particular styrene, acrylonitrile, methyl methacrylate, vinyl chloride and vinyl acetate, is carried out at temperatures below 0 ° C under the initiating effect of redox systems, e.g. mixtures of cumene hydroperoxide with sulfur dioxide or diethylsulphide at -10 to -40 ° C (tal. 788 100; ECN 16, No. 461, 36 (1971)) or ascorbic acid, heavy metal salt and hydrogen peroxide, with initiation at -8 to -50 ° C (NSR Pat. 1,213,119 and DAS 1,720,481); Technically and economically, it is even more attractive. a process for the polymerization of vinyl chloride to syndiotactic PVC with a heat resistance of up to 95 ° C, by suspension polymerization of vinyl chloride at 15 ° C, under the initiating effect of dilauroyl peroxide together with Fe (OH) ₂ , respectively. (C 2 ^H 11 ^C 2) 2 ^Fe £ Shareckij AM, Svetozarskij SV, Kotljar IB, Zilbermann EN: Vysokomolek. soed., ser. B, 12 (6), 476 (1970): U.S. Pat. 3,594,359j, or even the target itself. • Despite the apparent attractiveness of these procedures, their problem is

- 2 either high consumption of frigocalories, technically demanding removal of metal compound residues from polymers, or demanding preparation of own initiators.

Also known are the processes of polymerization or copolymerization of vinyl monomers by the initiation effect of dialkyl peroxydicarbonates formed directly in the reaction medium in situ from starting alkyl chloroformates, hydrogen peroxide and alkaline metal or earth hydroxides with vigorous modifications (U.S. Pat. No. 3,022,281; U.S. Pat. 869, 163 502, 172 662, Ϊ72 673 and 175 738 (Israel Pat. 29 131 and French Pat. 1 539 930), but the practically usable temperature is a rope in the range of 30 to 70 ° C. At lower temperatures, both percarbonates and altered peroxides of the formula ROCOOOCOR 'are almost ineffective. They partially solve the situation with chlorinated percarbonates formed in situ from chlorinated alkyl- or cycloalkyl chloroformates, in particular 2-chloroethyl chloroformate, hydrogen peroxide and alkali metal hydroxide. aut. lighting. 172,662). In this case, however, it is mainly based on the ease of preparation of both the starting materials and the peroxides proper, but mainly in their multi-functional action. An extreme case is the polymerization of vinyl monomers, in particular vinyl chloride, at -25 to -35 ° C, with the initiating effect of trichloroacetylperoxide, prepared in eit from trichloroacetyl chloride and NagOg (UK. Five. 975 861), but having a low yield as swallowable. initiators, as well as polymers.

However, it is sought to provide initiator solutions which, under technically manageable conditions, without high energy requirements, are able to initiate and ensure the production of polymers and provide an extremely high polymerization stage, or at steady-state polymerization temperatures to ensure a steady flow, and allow uniform heat release. optimal use of the cooling system and polymerization space and polymers of good quality.

These problems are solved by the method of radical polymerization and / or copolymerization of olefinically unsaturated monomers, preferably vinyl monomers, at normal or elevated pressure, at a temperature of -30 to 80 ° C, and preferably in suspension, with the initiating effect of organic peroxides formed and preferably in a polymerization and / or copolymerization reaction medium;

(a) hydrogen peroxide and alkaline hydroxide; and / or

(b) hydrogen peroxide and a weak acid alkali salt; and / or

e) alkali metal and / or earth peroxides, furthermore organic compounds containing at least one group per molecule. 0,

if X represents a halogenate, preferably chlorine, in an amount of 0.001 to 5% by weight, and preferably 0.01 to 0.5% by weight, calculated on the weight of the monomer or monomers, also in the presence of excipients, such that an organic compound or compounds containing at least one group in the molecule

- of aa adds at least one 2-chloroacetyl halide by a number of carbon atoms in the molecule of 3 to 12, preferably 3 to 6, or a mixture of at least one 2-chloroacyl and196839 cycloalkyl with C ₂ monoolefins also conjugated

- 3 logenides with at least one alkyl chloroformate and / or carbon number 2 to 12.

Suitable olefinically unsaturated monomers include up to C ^ ₂ , C8 to ^C12 diolefins having isolated double bonds, diolefins, but in particular vinyl monomers such as vinyl chloride, vinylidene chloride, acrylonitrile, styrene, vinyl esters such as vinyl acetate, methyl methacrylate and other esters of acid methacrylate and other esters and its esters, acrylamide and the like. Also included are trichlorethylene, maleic anhydride and esters of maleic acid and other unsaturated acids. Own initiator, organic peroxide, resp. The peroxide mixture can be formed from the starting materials directly in the reaction medium, respectively. in an in situ polymerization and / or copolymerization environment, optionally in a feed line, or in a separate device in the form of solutions, preferably in organic solvents, e.g. podl'a čs. aut. OAV. 175 908.

In particular, excipients other than solvents are known protective colloids, dispersants, emulsifiers, molecular weight regulators, antioxidants, pH regulators, particle modifiers, external and internal lubricants, plasticizers, alcohols, higher fatty acid salts, partially esterified polyols, partially saponified fats, partially saponified polyvinyl acetate etc.

Organic compounds containing at least one - C group in the molecule to form their own initiator in situ are up to alpha-chloroacyl halides, respectively. 2-chloroacetyl halides, preferably C 1 -C 2, but especially CH ₃ CH ₂ CH (Cl) COCl and CH ₃ CH (Cl) COCl, with at least 2-chloropropionyl chloride being the others. technically quite readily available. In the case of polymerization, respectively. copolymerization at temperatures of -30 to 30 ° C, the more efficient diacylperoxides are chlorinated at α-positions, for higher temperatures, mainly to achieve a steep start of polymerization or copolymerization and then a uniform flow with a rapid termination. starting HgO 2, alkali metal hydroxides and the like) from -chlorinated acyl chlorides and alkyl chloroformates, 2-chloroethyl ethyl and other generally known chloroformates C ₂ to C ₂ . In the case of dosing of chlorate acyl chlorides and chloroformates, it is advisable to add them in the form of solutions in solvents which can fulfill another function in the polymerization or copolymerization system (e.g. a molecular weight regulator), or at least in a portion of the monomer, respectively. monomers. In the case of solutions of organic peroxides already formed, it is advisable to ensure that the solvent also fulfills another function in the free radical reaction environment or at least has no retarding or other undesirable effect.

Advantages of the process according to the invention are both readily available starting materials, including X.-chlorinated acyl chlorides and chloroformates, their easy and safe shelf life, and flexibility in the preparation of different types of initiators, depending on the molecular weight requirements of the polymers, cooling efficiency, as well as polymer production needs. Furthermore, it is also possible to carry out the reaction at the technically and at least energy-efficient reaction temperatures, e.g. in the range of 10 to 30 ° C, to produce polymers and copolymers with an extra high of 196839

- 4 molecular masses and high heat resistance. Last but not least, the advantage is the possibility? Use? for such production conventional polymerization equipment. Other advantages as well as details of the method of the invention are apparent from the examples.

Example 1

Into a 300 cc stainless steel vial and 120 cc of an aqueous solution of methyl hydroxypropylcellulose of conc. 0.2% by weight, followed by aqueous NaOH with conc. 4.14 wt. (0.002 mole) and 0.7 cm @ aqueous H> 0 ₂ of the cone. 4.8 wt. (0.001 mol). 60 g of vinyl chloride (VC) was metered in after the air was purged with nitrogen. The entire vial was cooled to -30 ° C and then 0.267 g of 2-chloropropionyl chloride with conc. 94.8 wt. (0.002 mol). Thereafter, the ampoule was placed in a temperature-controlled bath at 20 ° C. After thawing of the aqueous phase, the reactants of the initiation and thymus reacted to give 0.358 wt.

CH-CHCOCl + 2 NaOH + H ₂ O ₂ * CH 3 CHCO-00-COCHCH 3 + 2 NaCl + 2 H ₂ Cl Cl bxs-2-chloropropionyl peroxide, calculated on vinyl chloride (VC), bj. 0.160 mol%. iniciátoraAC. The moment of insertion of the vial into the tempered bath was considered to be zero polymerization time. The polymerization was carried out with constant rotation of the vial. After a predetermined time, the vial was withdrawn, quenched to -30 ° C and its contents were removed, unreacted VC evaporated, homopolymer aa filtered, washed with distilled water, dried under reduced pressure at 50 ° C and weighed. determined the value of the euepensive PVC obtained, which was 113 ± 4. The extractable PVC content as a function of the polymerization time is shown in Table 1.

Table 1

J Polymerization time [hj 0.5 1 2 3 4 5 6 7 8 9 PVC Extract 03 3 6 17 29 41 53 64 70 76 81

Example 2

The procedure was similar to Example 1, except that the temperature of the tempered bath was 40 ± 0.2 ° C. The PVC product had a value of 84 + 2.

- 5 196839

TabuTka 2

Polymerization time 0.5 1 1.5 2 2.5 3 3.5 Yield of PVC [% J] 13 26 38 48 63 76 82

Example 3

In a 10 dm < 2 > stainless steel autoclave equipped with an anchor stirrer (200 rpm) and added 5,500 g of demineralized water and an additional 200 g of an aqueous solution of methylhydroxypropylcellulose with conc. 2 wt. Then 56.6 g of aqueous NaOH solution with conc. 3.3 wt. (i.e., 4.8.10 mol) ^and 25.5 g of an aqueous solution of H 2 O 4 with conc. 3.2 wt. (= 2.4.10 mol). The autoclave was then sealed, flushed with nitrogen thoroughly, and 5.23 g of 2-chloropropionyl chloride with conc. 97% wt. (i.e., 5.079 g as 100% = 4.0.10 mol). The contents of the autoclave were stirred for 1 1/2 hours. was heated to 50 ° C. From the moment of reaching this temperature, the polymerization time was calculated. After a predetermined polymerization time, the autoclave was rapidly cooled and the product content was discharged into a vessel from which unreacted VO was evaporated. The obtained PVC suspension was isolated by filtration and thoroughly rinsing with demineralized water. It was then dried at about 50 ° C and reduced pressure. Achieved results of suspension PVC yields since polymerization, resp. temperatures of 50 ° C are given in Table 3.

TabuTka 3

Polymerization time [hj 0 0.5 1 2 3 4 Yield PVC 17 30 34 37 38 38

Example 4

The procedure was similar to Example 3 except for 4.0. 10 moles of 2-chloropropionyl chloride (β-chloropropionyl chloride) were used equal molar amounts of other 2-chloroacetyl chlorides (β-chloroacetyl chlorides) The results obtained for PVC yields since the polymerization and the 2-chloroacetyl chloride type are shown in Table 4.

- 6 TABLE 4

2-Chlóracylchlorid time polymerisation vc [h3 PVC yield [t] 2-Chlorobutyryl chloride 0 0.5 1 2 3 4 14 26 29 31 32 32 0 1 3 4 - - 2-Gnloricapryioyicnioria 2 3 3 3 - - 2-Chlórpelargoylchlorid 0 1 3 4 - - tracks 1 1 1 - -

Example 5

For comparison with the results of Examples 3 and 4, in this example, previously prepared in toluene solution were used instead of in situ organic peroxides formed. The following organic peroxides were retested: bis- (2-chloropropionyl) - peroxide, bis- (2-chlorobutyryl-) peroxide and bis- (-2-chloropentyl * 2 goyl-) peroxide. The amount was 2.0 in all cases. 10 molu.

The autoclave was specified in Example 3. 5,500 g of demineralized water and 200 g of an aqueous solution of methylhydroxypropylcellulose with conc. 2 wt. and 2.0 was added to the batch while cooling the autoclave. 10 ~ 2 moles of organic peroxide in toluene solution, 3000 g of vinyl chloride were added and the stirrer was started. The contents of the autoclave were equally heated to 50 ° C over 1 1/2 h. The point at which this temperature was reached was considered to be zero polymerization time, although, understandably, polymerization generally began already during the heating of the autoclave content. After a predetermined period of time, the contents of the autoclave were rapidly cooled and quantitatively discharged into an open vessel from which the unreacted VC was evaporated. The obtained PVC suspension was filtered off; washed three times on the filter with demineralized water and dried under reduced pressure at 50 ° C. The PVC yield was then weighed and calculated. The results of PVC yields depending on the type of organic peroxide and polymerization time are given in Table 5.

Table 5

Peroxide species Polymerization time VC Ehil —--- ------------ '^ PVC yield O] bie - (- 2-chloropropionyl) * peroxide 0 0.5 1 2 3 4 22 38 41 43 44 44

- Ί 196839

Tab. 5

Peroxide species Polymerization time VC Ch J ---—  - PVC yield |> í bis - (- 2-chlorobutyryl) -peroxide 0 0.5 and 2 3 4 24 7 36 39 41 42 42 bis - (- 2-chlorobutyryl) -peroxide 0 0.5 1 2 3 24 36 39 41 42 42 bis - (- 2-chlórkapryloyl) -peroxide 0 0.5 1 2 3 - 25 ; 35 3R 39 39 bis - (- 2-chlórpelargoyl) -peroxide 0 0.5 .1. Second 3 - 27 34 17 U) 38 -

Example 6

The procedure was similar to that of Example 1, except that instead of homopolymerization, 2,550 g of vinyl chloride with 450 g of vinyl acetate were copolymerized and bia - (- 2-chloropropionyl -) - peroxide was also used in an amount of 2.0 · 10 mol. When the temperature reached 50 ° C, the copolymer yield was 29%, after 1 h 49% and after 3 h ‘> 7%.

Example 7

The procedure was similar to that of Example 1 except that 30 g of vinylidene chloride and 30 g of vinyl chloride were used instead of 60 g of vinyl chloride. The copolymer yield, respectively. also homopolymers mixtures reached 21% after 1 h, 69% after 5 h and 83% after 7 h. '

Example 8

The autoclave specified in Example 3 was used. The charge of the aqueous phase, the fault of chloride, NaOH and H ₂ O was also the same as that of Example 3. However, there was a fundamental difference in the type of chlorinated aeyl chlorides respectively. alkyl chloroformates, so that not only individually but also mixed peroxides could be formed in the polymerization environment.

The procedure was such that after the aqueous phase was fed into the autoclave and the air was purged with nitrogen, the necessary amount of chloroacetyl chloride and alkyl chloroformate was metered into the autoclave at a flow rate of 3000 g. During dosing of all

196839 - 8 of these components into the autoclave and its contents are thoroughly mixed with an anchor stirrer (200 rpm) and heated at 50 ° C evenly over 1 1/2 h after dosing. After the polymerization time has elapsed, the contents of the autoclave are suddenly cooled and simultaneously discharged into an open vessel in a fume hood where the VC is evaporated. Then, the PVC slurry is filtered, washed thoroughly, dried under reduced pressure, weighed and the homopolymer yield calculated.

The results obtained for PVC yields depend on time, but at least on the amount of chlorinated acyl chlorides and alkyl chloroformates as starting components of the initiators formed in situ, with an otherwise constant content of 4.8. 10 ^-2 mole of NaOH and 2.4. 10 ^"2 mole HgOg are shown in Table III sixth

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- 9 196839

Example 9

A 50 dm 2 autoclave equipped with an anchor stirrer (150 rpm) was charged with 27 kg of demineralized water and 1000 g of an aqueous solution of methylhydroxypropylcellulose with conc. 2% by weight, followed by 0.24 mol of NaOH and 0.12 mol of HgOg in the form of aqueous solutions. The air was then removed, 15 kg of vinyl chloride were introduced and 0.1 mol of 2-chloropropionyl chloride and 0.1 mol of isopropyl chloroformate were added to the stream during the addition of aa. The polymerization temperature reached 50 ° C during 1 1/2 h with continuous stirring and after a further 0.5 µl the polymer yield was 23.

Under otherwise similar conditions, except that 2-chloropropionyl chloride and isopropyl chloroformate were not added to the stream of vinyl chloride, but were previously dissolved in 2 kg of vinyl chloride, which were put in advance while stirring the autoclave and then the remaining 13 kg, for 0.5 h conversion of vinyl chloride reached 18%.

In the third case, 12 kg of vinyl chloride was added first with stirring and then the remaining 3 kg together with chloropropionyl chloride and isopropyl chloroformate. In this case, the conversion of vinyl chloride within 0.5 h to 50 ° C reached 29%.

Example 10

The procedure was similar to that of Example 7, the differences being only in monomers (2 800 g but instead of 3 000 g vinyl chloride but 200 g propylene) and in the amount of starting components of the initiator system were used three times more (i.e. , 44 -10 ^"1 mole of NaOH;

7.2. 10 ” ² moles H ₂ 0 ₂ ; 3. 10 ² mol of 2-chloropropionyl chloride and 9. 10 &lt; ^{2 &gt;} mole of isopropyl chloroformate). copolymer 32%, 6 £ 57% and 10 £ 84% each, with a K value of 58 + 2.

Example 11

In an analogous manner to Example 3 and using the same autoclave of 10 dm, an experiment was performed. The only difference was that sodium peroxide in the amount of 2.4 was used instead of sodium hydroxide -2 and hydrogen peroxide. 10 mol in the form of a solid of 95% purity and weighed 2,0 g. Weighed 4.0. 10 ² moles of 2-chloropropionyl chloride, 3 000 g vinyl chloride,

200 g of an aqueous solution of methylhydroxypropylcellulose (Methocel 50 F) at a concentration of 2% by weight and 5,000 g of demineralized water. The polymerization temperature was 50 ± 0.2 ° C. A yield of 315 g of suspension polyvinyl chloride was obtained over a period of 16%, corresponding to a yield of 10.5%.

- 10 Example 12

The procedure was similar to that in Example 3 except that sodium bicarbonate NaHCO 3 was used in an amount of 4.8 instead of sodium hydroxide as one of the starting components of initiator formation. 10 ^-2 mole. Heating also took 1.5 hours, while polymerizing at 50 ° C for 1 hour, 360 g of suspension polyvinyl chloride was obtained, corresponding to a polymer yield of 12.0%.

Example 13

Using the autoclave specified in Example 3 as well as a similar process to that of Example 3, suspension polymerization of methyl methacrylate was performed instead of vinyl chloride. The autoclave charge consisted of 5 500 g of demineralized water, 600 g of an aqueous solution of 2% by weight methylhydroxypropylcellulose, 4.8. 10 mol of sodium hydroxide, 2.4. 10 ^"4 mol of hydrogen peroxide 2 000 g of distilled methyl methacrylate and čeratvo 4.0. 10 ^"2 mole of 2-chloropropionyl chloride. 603 g of polymethyl methacrylate (i.e., 30.1% yield) was obtained in the polymerization over 1 hour, which was dissolved in toluene and precipitated with methanol and dried for 48 hours under reduced pressure at 55 ° C.

Example 14

The procedure was similar to that of Examples 3 and 13, except that methyl methacrylate in an amount of 1500 g and vinyl acetate in an amount of 500 g were used as monomers. 2-chloropropionyl chloride in an amount of 4.0. 10 ^-2 moles were metered into the aqueous phase as a methyl methacrylate solution (in 150 g methyl methacrylate) and after 5 min. the remaining methyl methacrylate and vinyl acetate were added. The copolymerization of ea was carried out at a temperature of 50 + 0.2, yielding 528 g of copolymer over 1 hour, corresponding to a yield of 26.4%.

Object of the invention

Claims (2)

Example 12 A similar procedure to Example 3 was followed, except that sodium bicarbonate NaHCO 3 at 4.8 was used as one of the starting components of initiator formation. 10-2 mole. Heating for 1.5 hours »360 g of suspension polyvinyl chloride were obtained during 1 h of polymerization at 50 ° C, δο corresponding to 12.0% of polymer yield. EXAMPLE 13 Using the Autoclave Specified in Example 3, as well as a similar technical procedure to Example 3, a suspension polymerization of methyl methacrylate was performed in place of vinyl chloride. The autoclave was charged with 5,500 gdemineralized water, 600 g of an aqueous solution of methylhydroxypropylcellulose at a concentration of 2%, 4.8. 10 mol of sodium hydroxide, 2.4. 10 ”4 moles of hydrogen peroxide, 2,000 g of freshly distilled methyl methacrylate and 4.0. 10-2 moles of 2-chloropropionyl chloride. During 1 h, 603 g of polymethyl methacrylate (¼}, yield 30.1%) was obtained by polymerization, which was dissolved in toluene and precipitated with methanol and dried at 48 ° C. under reduced pressure at 55 ° C. Example 14 A procedure similar to that of Examples 3 and 13 was followed, except that the monomers used were methyl methacrylate at 1500 g and vinylacetate at 500 g, while 2-chloropropionyl chloride was 4.0. 10 ~ 2 molus dispensed into the aqueous phase in the form of methyl methacrylate solution (in 150 g methyl methacrylate) and after 5 min. the remaining methyl methacrylate and vinyl acetate were added. The copolymerization was carried out at 50 + 0.2, with 528 g of copolymer being obtained over 1 h, δο corresponding to a yield of 26.4%. The object of the invention A process for the radical polymerization and / or copolymerization of olefinically unsaturated monomers, preferably vinyl monomers, at normal or elevated pressure, at a temperature of -30 to 80 ° C, preferably in suspension, with the initiation effect of organic peroxides, preferably formed in the reaction medium. - polymerization and / or copolymerization, with: hydrogen peroxide and alkali hydroxide and / or b) hydrogen peroxide and alkali salt of weak acid and / or c) alkali metal and / or earth peroxides, furthermore organic compounds containing at least one molecule in the molecule - 11 - 196839 - where X is a halogenate, preferably chlorine, in an amount of 0.001 to 5% by weight, preferably 0.01 to 0.5% by weight, based on the weight of the monomer or monomers; the presence of excipients, characterized in that at least = = θ, one group - C is added as an organic compound or compounds containing in the molecule at least one 2-chloroacyl halide having a carbon number of 3 to 12, preferably 3 to 6, or a mixture of at least one 2-chloroacyl halide with at least one alkyl and / or cycloalkyl chloroformate having 2 to 12 carbon atoms. 2. Process according to claim 1, characterized in that the 2-chloroacyl halides, preferably of the formula CH 2 CH 2 Cl 2 COCl 2 and CH 2 CH 2 CH 2 CH 2 Cl 2 COCl 3, or 2-chloroacylhalides with alkyl and / or cycloalkyl chloroformates, is brought into contact with other organic constituent components, preferably into the polymerization and / or copolymerization, individually concentrated compounds or in a mixture, preferably at least partially dissolved in the monomer or monomers, optionally in an organic solvent .