WO1981002299A1 - Vinyl chloride polymers - Google Patents

Vinyl chloride polymers Download PDF

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Publication number
WO1981002299A1
WO1981002299A1 PCT/NL1981/000001 NL8100001W WO8102299A1 WO 1981002299 A1 WO1981002299 A1 WO 1981002299A1 NL 8100001 W NL8100001 W NL 8100001W WO 8102299 A1 WO8102299 A1 WO 8102299A1
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WO
WIPO (PCT)
Prior art keywords
solvolysis
degree
vinyl chloride
weight
monomer
Prior art date
Application number
PCT/NL1981/000001
Other languages
English (en)
French (fr)
Inventor
P Lemstra
Original Assignee
Stamicarbon
P Lemstra
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stamicarbon, P Lemstra filed Critical Stamicarbon
Publication of WO1981002299A1 publication Critical patent/WO1981002299A1/en
Priority to NO813357A priority Critical patent/NO156453C/no

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride

Definitions

  • the invention relates to a process for the suspension polymerization of vinyl chloride, if so desired with one or more copolymerizable monomers, with monomer-soluble, radical-forming initiators, and in the presence of suspending agents, to vinyl chloride polymers with at least 70 % by weight of vinyl chloride units having good processing properties.
  • the suspension polymerization of vinyl chloride if so desired with copolymerizable monomers, is generally known and is carried out extensively on a technical scale.
  • Liquid vinyl chloride is suspended in water and polymerized with monomer-soluble, radical-forming initiators at temperatures of between 30 °C and 80 °C.
  • the polymerization takes place in the monomer droplets.
  • Usual initiators are lauroylperoxide, dialkylpercarbonates, specifically diisopropylpercarbonate, azo compounds, specifically azo-bis-isobutyronitrile, sulphonyl peroxides, specifically acetylcyclohexanesulphonylperoxide.
  • Suspending agents are used in order to promote and to stabilize the distribution of monomer or monomers in the aqeous phase and in order to prevent the agglomeration of polymer particles during the polymerization.
  • Usual suspending agents are gelatine, cellulose derivatives, polyvinyl alcohols and polymeric suspending agents based on maleic acid or acrylic acid, for instance copolymers of maleic acid and vinyl acetate.
  • Vinyl chloride Since the toxious properties of vinyl chloride have become known, the demands on the removal thereof from the polymer have increased. Vinyl chloride has been found to be easier to remove from the polymer as the porosity increases. High porosity of the polymer often goes with a low bulk density. At a given porosity, however, the bulk density has been found to differ. As the bulk density increases, the processability, particularly the throughput in extruders, improves. The purpose, therefore, is to prepare vinyl chloride polymers of which the bulk density at a certain, desired porosity is as high as possible.
  • the choice thereof is particularly important. By modification of the suspending agents it is tried to ever further improve the properties of the polymers to be prepared.
  • vinyl chloride polymers having good porosity, a large BET surface area, a narrow particle size distribution, few fish eyes in processing, and good plasticizer take—up can be prepared by suspension polymerization of vinyl chloride, if so desired with copolymerizable monomers with monomer-soluble, radical-forming initiators, in the presence of primary and secondary suspension agents, by carrying out the polymerization in the presence of 0.005-0.5 parts by weight of a primary suspending agent known as such per 100 parts by weight of monomer and as secondary suspending agent 0.005-0.5 parts by weight, per 100 parts by weight of monomer, of a polyvinyl alcohol with a degree of polymerization of at least 250 and preferably at least 350, with a degree of solvolysis of 40 to 70 moles % and with a narrow distribution of the degree of hydrolysis.
  • a polyvinyl alcohol with a degree of solvolysis of 70 to 90 moles % is preferably used
  • polyvinyl alcohols characterized by, among other things, a certain degree of solvolysis, and used as suspending agents, are prepared by solvolysis of polyvinyl acetate, because polyvinyl alcohol cannot be directly prepared by polymerizatipn. of vinylalcohol, which is tautomeric with acetaldehyde.
  • polyvinyl acetate can be converted, with an acid or an alkali as catalyst, into polyvinyl alcohol.
  • solvolysis comprises both conversions.
  • the solvolysis may be effected completely or partially.
  • a partially solvolyzed polyvinyl alcohol can be regarded as a copolymer of vinyl acetate and vinyl alcohol, but is in practice referred to as polyvinyl alcohol, with the degree of hydrolysis, or better the degree of solvolysis, being stated.
  • the effect of the secondary suspending agents such as polyvinyl alcohol with a degree of solvolysis of 40 to 70 moles %-, preferably 50 to 60 moles %, and a narrow distribution of the degree of hydrolysis, is explained in the Netherlands patent application 7714034, from the presumption that this secondary suspending agent is forced into the boundary surface of the vinyl chloride monomer and the water, so that it very favourably influences the structure of the PVC to be formed.
  • the method described there shows a great disadvantage.
  • the polyvinyl alcohol with a degree of solvolysis of 40 to 70 moles %, more in particular 50 to 60 moles %, with a narrow distribution of the degree of hydrolysis, to be used as secondary suspending agent is expensive.
  • Polyvinyl acetate is to be understood as a polymer of vinyl acetate which is hardly solvolyzed and therefore has a degree of solvolysis of 2-14 moles %, often even of 3-12 moles %. It is surprising that such a relatively cheap polyvinyl acetate with a low degree of solvolysis, which can no longer act as a suspending agent, because the number of hydroxyl groups contained in it are too small for this purpose, has an even better effect as an expensive secondary suspending agent as described in the Netherlands patent application 7714034.
  • this polyvinyl acetate may contain minor quantities of other monomers incorporated by polymerization, e.g. to 20 % by weight.
  • Usual primary suspending agents are gelatin, polymeric suspending agents based on maleic acid or acrylic acid, for instance copolymers of maleic acid and vinyl acetate.
  • Very suitable primary suspending agents are polyvinyl alcohols with a degree of solvolysis of 70 to 90 moles % and cellulose derivatives, specifically hydroxypropyl cellulose, methylhydroxypropyl cellulose and hydroxyethyl cellulose. Very suitable also are mixtures of the above polyvinyl alcohols and/or cellulose derivatives.
  • the invention is further elucidated by the following nonrestrictive examples and comparative experiments.
  • An enameled autoclave of 100 1 is filled with 26.0 kg vinylchloride, 36.4 kg water, 15.6 g polyvinyl alcohol with a degree of solvolysis of 79 moles % and a degree of polymerization of 1700 and 10.4 g polyvinyl acetate with a low degree of solvolysis and a degree of polymerization of 330, the degree of solvolysis being about 5 moles %.
  • the whole While being stirred, the whole is heated to 330.5 K and is kept at this temperature until the pressure in the autoclave, which was about 950 kPa, falls to about 800 kPa. The pressure is subsequently relieved and the polymerization is discontinued. The polyvinyl chloride is subsequently recovered from the suspension and is dried. Of this polyvinyl chloride the bulk density, the average particle size and the porosity are determined.
  • the average particle size (d) is determined by the sieve analysis method described by Rosin and Rammler in Kolloid Zeitschrift 67 (1934)), pages 16-26, and Chem. Ing. Tech., 24 (1942), pages 25-31.
  • the porosity ( ⁇ ) is determined by the mercury intrusion method at a pressure of 12 MPa. L.A. de Wit and J.J.F. Scholten, J. Cat. 36 (1975), pages 36-47, give a general exposition of the theory of this method and Guyer, Bohlen and Guyer, Helv. Chim. Acta 42 (1959), page 2103, describe an apparatus for the measuring of the porosity according to this method.
  • vinyl chloride is polymerized, except that polyvinyl acetate with a low degree of solvolysis and a degree of polymerization of 1480, the degree of solvolysis being about 5 moles %, is used.
  • Example 3 In a way similar to that of example 1, vinyl chloride is polymerized, except that polyvinyl acetate with a low degree of solvolysis and a degree of polymerization of 3470, the degree of solvolysis being 5 moles %, is used.
  • vinyl chloride is polymerized, except that, instead of 10.4 g, 20.8 g of the same polyvinyl acetate with a low degree of solvolysis is used.
  • Example 5 In a way similar to that of example 2, vinyl chloride is polymerized, except that, instead of 10.4 g, 20.8 g of the same polyvinyl acetate with a low degree of solvolysis is used.
  • a d of 150 ⁇ m, an ⁇ of 0.30 x 10 -3 m 3 /kg and a bulk density of 480 kg/m 3 are found for the polyvinyl chloride.
  • vinyl chloride is polymerized, except that, instead of 10.4 g, 20.8 g of the same polyvinyl acetate with a low degree of solvolysis is used.
  • vinyl chloride is poly merized, except that, instead of polyvinyl alcohol, hydroxypropyl cellulose and, instead of 10.8 g, 15.6 g of the same polyvinyl acetate with a low degree of solvolysis is used.
  • a d of 160 ⁇ m, an ⁇ of 0.25 x 10 -3 m 3 /kg and a bulk density of 517 kg/m 3 are found for the polyvinyl chloride.
  • vinyl chloride is polymerized, except that no polyvinyl acetate with a low degree of solvolysis is added, but, instead, 20.8 g of a secondary suspending agent, viz. a polyvinyl alcohol with a degree of solvolysis of 55 moles % and a degree of polymerization of 580 and with a narrow distribution of the degree of solvolysis, i.e. more than 80 % has a degree of solvolysis of between 45 and 65 moles % (which does behave as a secondary suspending agent).
  • a secondary suspending agent viz. a polyvinyl alcohol with a degree of solvolysis of 55 moles % and a degree of polymerization of 580 and with a narrow distribution of the degree of solvolysis, i.e. more than 80 % has a degree of solvolysis of between 45 and 65 moles % (which does behave as a secondary suspending agent).
  • vinyl chloride is polymerized, except that, as secondary suspending agent, an otherwise identical polyvinyl alcohol with a degree of polymerization of 1450 is used.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/NL1981/000001 1980-02-05 1981-02-05 Vinyl chloride polymers WO1981002299A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
NO813357A NO156453C (no) 1980-02-05 1981-10-02 Fremgangsmaate ved fremstilling av vinylkloridpolymerer.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL8000707 1980-02-05
NL8000707A NL8000707A (nl) 1980-02-05 1980-02-05 Vinylchloridepolymeren.

Publications (1)

Publication Number Publication Date
WO1981002299A1 true WO1981002299A1 (en) 1981-08-20

Family

ID=19834782

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1981/000001 WO1981002299A1 (en) 1980-02-05 1981-02-05 Vinyl chloride polymers

Country Status (6)

Country Link
EP (1) EP0033577B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPS57500245A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
AT (1) ATE10636T1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE3167532D1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NL (1) NL8000707A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO1981002299A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL8301462A (nl) * 1983-04-26 1984-11-16 Stamicarbon Vinylchloridepolymeren.
NL8301463A (nl) * 1983-04-26 1984-11-16 Stamicarbon Vinylchloridepolymeren.
IT1210541B (it) * 1986-02-17 1989-09-14 Paolo Carlin Procedimento per la produzione in emulsione acquosa di polivinile acetato parzialmente idrolizzato.
IT1235098B (it) * 1989-06-15 1992-06-18 Francesco Carlin Procedimento per la produzione in emulsione acquosa di miscele di alcoli polivinilici e prodotti cosi' ottenuti.

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4923231A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1972-06-23 1974-03-01
JPS5291089A (en) * 1976-01-28 1977-08-01 Shin Etsu Chem Co Ltd Preparation of vinyl chloride polymers
FR2341600A1 (fr) * 1976-02-17 1977-09-16 Sigma Italiana Prod Chimici Procede de fabrication du chlorure de polyvinyle

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7714034A (nl) * 1977-12-19 1979-06-21 Stamicarbon Vinylchloridepolymeren.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4923231A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1972-06-23 1974-03-01
JPS5291089A (en) * 1976-01-28 1977-08-01 Shin Etsu Chem Co Ltd Preparation of vinyl chloride polymers
FR2341600A1 (fr) * 1976-02-17 1977-09-16 Sigma Italiana Prod Chimici Procede de fabrication du chlorure de polyvinyle

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts, vol. 83, no. 16, issued October 20, 1975, (Columbus, Ohio, US), Ito Koreatsu: "Suspension polymerization of Vinylchloride ", page 28, column 1, abstract no. 132307d; & JP-A-49 023 231, June 18, 1974, (Sumitomo Chemical Co.) *
Chemical Abstracts, vol. 87, no. 22, issued November 28, 1977, (Columbus, Ohio, US), Kurimoto: "Poly(vinylchloride)", page 15, column 1, abstract no. 168617b; & JP-A-52 091 089, August 1, 1977, (Shin-Etsu Chemical Industry Co. Ltd.) *

Also Published As

Publication number Publication date
ATE10636T1 (de) 1984-12-15
EP0033577A1 (en) 1981-08-12
EP0033577B1 (en) 1984-12-05
DE3167532D1 (en) 1985-01-17
NL8000707A (nl) 1981-09-01
JPS57500245A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1982-02-12

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