EP0619829A1 - A polyvinyl chloride ready for processing and its preparation method - Google Patents

A polyvinyl chloride ready for processing and its preparation method

Info

Publication number
EP0619829A1
EP0619829A1 EP93900213A EP93900213A EP0619829A1 EP 0619829 A1 EP0619829 A1 EP 0619829A1 EP 93900213 A EP93900213 A EP 93900213A EP 93900213 A EP93900213 A EP 93900213A EP 0619829 A1 EP0619829 A1 EP 0619829A1
Authority
EP
European Patent Office
Prior art keywords
olefin
polymer
polymerization
oligomer
processing
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
EP93900213A
Other languages
German (de)
English (en)
French (fr)
Inventor
Hannu Harjuhahto
Henrik Holmqvist
Esa Karhu
Leif Rockas
Tommy NÄS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topvin Oy
Original Assignee
Topvin Oy
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 Topvin Oy filed Critical Topvin Oy
Publication of EP0619829A1 publication Critical patent/EP0619829A1/en
Ceased legal-status Critical Current

Links

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
    • C08F214/00—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
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/06—Vinyl chloride
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment

Definitions

  • the invention relates to a vinyl chloride, which is directly ready for processing, and in which the necessary processing additives, such as stabilizers, lubricants, colourants and reinforcing agents, etc., are added to the polymer in the polymeri ⁇ zation reactor.
  • the invention also relates to a method for preparing such a vinyl chloride polymer.
  • Polyvinyl chloride is pricewise an economical thermoplastic suitable for a large number of applications.
  • one or more stabilizers, lubricants, pigments and/or modifiers are to be added to the resin obtained in the polymerization.
  • the polymer purchased by him/her would be as ready as possible for processing.
  • this requires the building of a separate mixing plant either after the polymerization reactor or at the plant of the end-product manufacturer.
  • Research work on the addition of additives, especially stabilizers, during the polymerization have been made and some patent publications are available.
  • polyoxazoline of a certain type is used as a suspension stabilizer, whereby organic or inorganic zinc compounds may be added to the polymerization reactor as prestabilizers.
  • the final stabilization is performed subsequently in a conventional manner.
  • the additives have been introduced into the polymerization reactor in connection with the bulk polymerization of vinyl chloride. According to the publication, conventional additives may be used.
  • the polymerization may also be a two-step polymerization, whereby the additives are added in the second step. E.g. stabilizers, lubricants and processing aids are added to the polymerization.
  • the homo- or copolymer composition according to the invention is characterized in that it has been prepared by adding into the polymerization reactor in the beginning of the polymerization, during it or at the end thereof 0.01-50 weight-% of the amount of vinyl chloride a liquid olefin oligomer and/or ethylene olefin copolymer or olefin terpolymer.
  • the liquid olefin oligomer may be a dimer, trimer, tetramer, pentamer or hexamer of ⁇ -olefins or internal olefins (C ⁇ -C ⁇ Q ) or their mixture, whereby the lengths of the carbon chains are C 2Q -C 10Q .
  • the oligomer may contain double bonds or it may be hydrated.
  • a liquid polymer may be used, which is an elastomeric ethylene propylene polymer, in which e.g. dicyclo pentadiene or ethylidene norbornene is used as the termonomer.
  • the liquid polymer may be used in addition to the oligomer or in place thereof.
  • the selection of the oligomer and/or the liquid polymer to be used depends on the desired end product.
  • the addition of the liquid oligomer and/or polymer into the polymerization reactor thus makes the addition of other additives possible in the beginning of the polymerization or during it, and a polymer ready for processing is obtained as a product.
  • PVC-polymers ready for processing prepared in the inventive method may be used for the same products as compounds prepared by means of a conventional polymerizing and mixing technique. They may be processed e.g. by extrusion, injection moulding, blow molding or calendering, and various products, such as pipes, pipe fittings, sheets, profiles and bottles may be prepared.
  • Suitable additives are the same as those used in the preparation of a conven- tional mixture.
  • stabilizers may be used lead compounds, such as lead sul ⁇ phate, -phosphite, -carbonate or -phtalate or barium/zinc-, calcium/zinc- or tin compounds.
  • costabilizers may be used lead-, calcium- or zinc stearates, epoxidized soyabean oils, epoxidized linsead oils or epoxidized fatty-acid esters.
  • fillers may be used e.g. calcium carbonates, kaolin, silica or aluminium hydroxide.
  • Suitable fire-retardant agents are e.g. antimony trioxide, zinc borate, zinc oxide or aluminium hydroxide.
  • external lubricants may be used e.g. lead-, calcium- or zinc stearates, fatty acids, fatty-acid esters, -alcohols or -amides, montan acid wax or -esters, paraffin-, hydrocarbon- or polyethylene waxes.
  • Suitable colourants are carbon black, titanium dioxide, various organic and inorganic pigments.
  • a processing aid e.g. a polymethyl methacrylate and as a reinforc- ing agent various polymers, such as acrylnitrile butadiene styrene (ABS), meth- acrylate butadiene styrene (MBS), chlorinated polyethylene (CPE), ethylene vinyl acetate (EVA) or various acrylate plastics.
  • ABS acrylnitrile butadiene styrene
  • MVS meth- acrylate butadiene styrene
  • CPE chlorinated polyethylene
  • EVA ethylene vinyl acetate
  • the polymerization is performed in a similar method as the conventional PVC preparation by the suspension polymerization method.
  • the vinyl chloride is dispersed in water by using e.g. polyvinyl alcohol (PVA) or cellulose derivatives as a suspending agent.
  • PVA polyvinyl alcohol
  • the initiator of the polymerization is an organic peroxide soluble in the monomer.
  • the polymerization tempera- ture may typically be 50-70°C and correspondingly the pressure 7-12 bar.
  • the polymerization time is most usually 4-8 hours. The length of the polymer chain is nearly totally determined according to the temperature.
  • the polymerization pressure starts to decrease.
  • the batch is transferred to a degassing or stripping container, in which the unpolymerized monomer is recovered and returned into the process.
  • the PVC-water mixture is dried, whereby part of the water is mechanically separated, the remainder by means of heat and finally, the product is screened.
  • the inventive polymerization differs from the conventional polymerization basically because of the fact that the oligomer and/or the liquid polymer as well as the additives normally to be mixed separately after the polymerization are introduced into the polymerization reactor already before the start of the polymerization, during it or after it in one or more steps.
  • the inventive method By using in the polymerization of vinyl chloride the inventive method, many advantages are reached in the process compared to the known technique.
  • the additives are introduced already in the polymerization step, the homogenous distribution of the additives is improved compared to that in the preparation of a conventional mixture, in which the additives are dry-mixed into the polymer before treatment.
  • the additives can be introduced into the polymerization reactor as a water solution or suspension, and thus the dusting problems, which occur during a conventional mixing process, are avoided.
  • the polymerization time decreases, when the degree of polymerization at high conversions increases as a result of a rapid pressure drop and a higher conver ⁇ sion rate is obtained.
  • the stripping conditions can be maintained harder in a batch-type stripping equipment, since the heat stabilizers have already been added to the polymer before the stripping. Then, the monomer emissions into the air and waste waters decrease and the raw-material balance is improved. The colouring and the thermal decomposition of the polymer during the stripping are completely avoided.
  • the economy of the drying step can be improved by using a higher inlet tem ⁇ perature and a higher temperature difference.
  • the energy consumption decreases because of the improved thermal efficiency.
  • the thermal decomposition during the drying can be avoided even at a temperature exceeding 100°C, since the heat stabilizers have been added already during the polymerization.
  • the screening step is intensified, since due to the metal-containing additives, the occurrence of static electricity decreases and smaller meshes may be used.
  • the fluidity of the final polymer is better due to a higher density and a higher granular size. As a result, the dusting problems of the final polymer decrease.
  • heavy metals such as lead
  • their amount can be decreased ( ⁇ weight-%) for a better distribution.
  • the polymerizations are performed in an autoclave-type polymerization reactor. Standard methods have been used for analyzation: volume weight: ISO R 60, viscosity number and K-value: ISO R 174, and softener absorption (DOP): ISO 4608.
  • a polymerization reactor Into a polymerization reactor was batched 10 kg of vinyl chloride (VCM) and 15 kg of water. Into the reactor was also added calcium stearate and lead sulphate or zinc stearate for stabilization. A dispersing agent (polyvinyl alcohol) was added in the beginning of the polymerization and during it. In addition to a dicetyl peroxide carbonate initiator, lauryl peroxide was also used. The oligomer was added in the beginning of the polymerization. The oligomer used was a hydrated decene oligomer, which mainly contained tetramer (C ⁇ ) and to some extent trimer ( ⁇ Q ) and pentamer (C 50 ). The polymerization recipes are shown in Table 1 and the results in Table 2.
  • VCM vinyl chloride
  • E-P liquid ethylene propylene polymer
  • the hydrated oligomer used was a mixture of tetramer (C 40 ) and pentamer (C 50 ) and the liquid polymer in the Examples 6 and 7 an ethylene propylene dicyclopentadiene terpolymer, in Example 8 an ethylene propylene norbornene terpolymer and in Example 9 an ethylene propylene copolymer.
  • the polymerization recipes are shown in Table 3 and the results in Table 4. Table 3.
  • the plant scale polymerizations have been performed with conventional polymerization reactors by using a technique used in the normal PVC prepara- tion, except that during the polymerization an oligomer of olefin and/or liquid ethylene propylene copolymer as well as other additives have been added.
  • a reference grade has been used a commercial resin, whose K-value is 68.
  • the additives used are shown in Table 5 and the resin analyses in Table 6.
  • Pipes ( ⁇ 110/3.2 mm) were prepared from the resins with a CM65 2-screw extruder. Conic screws: diameter 65/120 mm, length 1210 mm, operating speed max. 34.4 rpm and total torsion 10.2 kNm.
  • Falling weight impact tests were performed for the pipes according to the standard SS3064.
  • the falling weight is 6.0 kg and the drop-weight tip diameter 25 mm.
  • the pipes were kept in a temperature of -10°C or -20°C for 24 hours before the performance of the falling weight test.
  • the reference grade is a PVC resin produced by a conventional method, into which PVC resin the stabilizers have been dry mixed.
  • the results of the falling weight tests are shown in Table 7. It can be observed from the results that the polymer prepared by the method is according to this invention by its impact strength extremely good and that the pipes manufactured therefrom are also very well suitable for cold conditions.
  • VCM vinyl chloride monomer
  • dispersing agent totally 1.4 kg of polyvinyl alcohol /kg of VCM.
  • dicetyl peroxide carbonate 1.3 g /kg VCM.
  • lead sulphate / kg VCM was added in the begmning of the polymerization.
  • the used oligomer was hydrated decene oligomer containing tetrames ( J Q ), pentamers (C 50 ) and heptamers (Cg g ). Oligomer was added:
  • Example 16 in the beginning of the polymerization reaction Example 17: during the reaction, 40 min from the beginning Example 18: during the reaction, before the pressure release Example 19: to the slurry, after gas removal
  • Polymerization was performed in the same method as in Example 16, except that the oligomer used was made from internal olefin mixture containing 90% C 15 olefin and 10% C 16 olefin.
  • the oligomer contained 47% of dimers, 40% trimers and 13% tetramers.
  • the polymerization results were:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP93900213A 1991-12-31 1992-12-23 A polyvinyl chloride ready for processing and its preparation method Ceased EP0619829A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI916191 1991-12-31
FI916191A FI95473C (fi) 1991-12-31 1991-12-31 Työstöön valmis polyvinyylikloridi ja sen valmistusmenetelmä
PCT/FI1992/000361 WO1993013145A1 (en) 1991-12-31 1992-12-23 A polyvinyl chloride ready for processing and its preparation method

Publications (1)

Publication Number Publication Date
EP0619829A1 true EP0619829A1 (en) 1994-10-19

Family

ID=8533760

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93900213A Ceased EP0619829A1 (en) 1991-12-31 1992-12-23 A polyvinyl chloride ready for processing and its preparation method

Country Status (19)

Country Link
EP (1) EP0619829A1 (enrdf_load_stackoverflow)
JP (1) JPH07506848A (enrdf_load_stackoverflow)
KR (1) KR940703868A (enrdf_load_stackoverflow)
CN (1) CN1075153A (enrdf_load_stackoverflow)
AU (1) AU3161193A (enrdf_load_stackoverflow)
BR (1) BR9207004A (enrdf_load_stackoverflow)
CA (1) CA2127103A1 (enrdf_load_stackoverflow)
CZ (1) CZ154194A3 (enrdf_load_stackoverflow)
EE (1) EE9400236A (enrdf_load_stackoverflow)
FI (1) FI95473C (enrdf_load_stackoverflow)
HU (1) HUT67926A (enrdf_load_stackoverflow)
LT (1) LT3256B (enrdf_load_stackoverflow)
LV (1) LV10114B (enrdf_load_stackoverflow)
NO (1) NO942385L (enrdf_load_stackoverflow)
RU (1) RU94031159A (enrdf_load_stackoverflow)
SI (1) SI9200418A (enrdf_load_stackoverflow)
SK (1) SK78194A3 (enrdf_load_stackoverflow)
WO (1) WO1993013145A1 (enrdf_load_stackoverflow)
YU (1) YU112392A (enrdf_load_stackoverflow)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY124060A (en) * 1999-01-11 2006-06-30 Ciba Holding Inc Synthetic polymers comprising additive blends with enhanced effect
US6251308B1 (en) * 1999-03-19 2001-06-26 Premix Highly conductive molding compounds and fuel cell bipolar plates comprising these compounds

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3862066A (en) 1971-05-26 1975-01-21 Universal Pvc Resins Method for making rigid vinyl chloride polymer compounds
US4031299A (en) * 1975-04-11 1977-06-21 Stauffer Chemical Company Process for forming a polyvinyl chloride extender resin by incorporating in the suspension polymerization medium a prehomogenized solution of a polyallyl compound and a low molecular polymer of propylene
ES459904A1 (es) 1976-06-17 1978-11-16 Hooker Chemicals Plastics Corp Un procedimiento de polimerizacion en masa en fase liquida para la produccion de un polimero de un haluro de vinilo.
DE3218173A1 (de) * 1982-05-14 1983-11-17 Chemische Werke Hüls AG, 4370 Marl Verfahren zur herstellung von polymeren und copolymeren des vinylchlorids durch suspensionspolymerisation und verwendung fuer den einsatz als viskositaetserniedriger in der plastisolverarbeitung
US4508863A (en) * 1983-07-06 1985-04-02 Argus Chemical Corporation Stabilization of polyvinyl chloride
DE3630318A1 (de) 1986-09-05 1988-03-10 Huels Chemische Werke Ag Verfahren zum stabilisieren von polyvinylchlorid oder bis zu 30 gewichtsprozent an comonomeren enthaltenden copolymeren des vinylchlorids

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9313145A1 *

Also Published As

Publication number Publication date
LT3256B (en) 1995-05-25
HU9401947D0 (en) 1994-09-28
JPH07506848A (ja) 1995-07-27
NO942385D0 (enrdf_load_stackoverflow) 1994-06-22
FI916191L (fi) 1993-07-01
NO942385L (no) 1994-06-22
SI9200418A (en) 1993-06-30
FI95473B (fi) 1995-10-31
BR9207004A (pt) 1995-10-24
EE9400236A (et) 1996-02-15
FI916191A0 (fi) 1991-12-31
WO1993013145A1 (en) 1993-07-08
HUT67926A (en) 1995-05-29
FI95473C (fi) 1996-02-12
YU112392A (sh) 1995-10-03
LV10114B (en) 1995-02-20
LTIP255A (en) 1994-10-25
AU3161193A (en) 1993-07-28
RU94031159A (ru) 1996-04-20
CA2127103A1 (en) 1993-07-08
KR940703868A (ko) 1994-12-12
CN1075153A (zh) 1993-08-11
LV10114A (lv) 1994-05-10
CZ154194A3 (en) 1994-11-16
SK78194A3 (en) 1995-02-08

Similar Documents

Publication Publication Date Title
EP0907677B1 (en) Process for enhancing the melt strength of propylene (co)polymers
US3454544A (en) Process for the chlorination of polyolefins
US6103833A (en) Process for enhancing the melt strength of polypropylene (co)polymers
AU1669399A (en) Extrusion process for enhancing the melt strength of polypropylene
HU219677B (hu) Nagy szilárdanyag-tartalmú polimerdiszperzió, valamint eljárás ilyen diszperzió előállítására
JPH06207054A (ja) 熱可塑性組成物、その製造方法及び使用
US6313228B1 (en) Peroxidic treatment of olefin polymers
CA1285694C (en) High bulk density pvc resin suspension polymerization
CA1056540A (en) Processing aid for polyvinyl chloride
EP0619829A1 (en) A polyvinyl chloride ready for processing and its preparation method
US3963687A (en) Two step continuous polymerization method to form acrylonitrile copolymers
US3030322A (en) Method of mixing polymeric hydrocarbons and waxes
US3468858A (en) Vinyl chloride-propylene copolymers
CA1218798A (en) Process for making dispersion copolymers through monomer metering
US3683051A (en) Copolymers of vinyl chloride and lower olefins
EP0137519A2 (en) Graft polymers of polymerizable monomers and olefin polymers
FI95474C (fi) Vinyylikloridipolymeeri
US4155954A (en) Method of grafting vinyl chloride onto ethylene-vinyl acetate and ethylene-alkyl acrylate copolymers
IL129691A (en) Process for preparing aqueous suspensions of a thermally unstable organic compound, the suspensions obtained by this process and the use of these suspensions in the polymerization of vinyl chloride
EP0991678A1 (en) Polyvinyl chloride, processes for its production, and compositions containing it
US5780564A (en) Method of preparing a homo-or copolymer of vinyl chloride containing .alpha.
US5973079A (en) Large particle generation
KR970065568A (ko) 발포특성이 우수한 염화비닐계 수지의 제조방법
CA2207785A1 (en) Large particle generation
US3715413A (en) VINYL CHLORIDE-PROPYLENE COPOLYMER GRAFTED WITH BUTADIENE, alpha -METHACRYLONITRILE AND OPTIONALLY STYRENE

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19940624

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI NL SE

17Q First examination report despatched

Effective date: 19960422

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 19981113