WO1991018032A1 - Copolymere d'ethylene/silane de vinyle et preparation de ce compose - Google Patents

Copolymere d'ethylene/silane de vinyle et preparation de ce compose Download PDF

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Publication number
WO1991018032A1
WO1991018032A1 PCT/FI1991/000099 FI9100099W WO9118032A1 WO 1991018032 A1 WO1991018032 A1 WO 1991018032A1 FI 9100099 W FI9100099 W FI 9100099W WO 9118032 A1 WO9118032 A1 WO 9118032A1
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WO
WIPO (PCT)
Prior art keywords
copolymer
hydroxy
polymer
monomer
ethylene vinyl
Prior art date
Application number
PCT/FI1991/000099
Other languages
English (en)
Inventor
Christer BERGSTRÖM
Markku Puropaasi
Torvald Vestberg
Ismo Lehtiniemi
Original Assignee
Neste 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 Neste Oy filed Critical Neste Oy
Priority to JP91506904A priority Critical patent/JPH05507098A/ja
Publication of WO1991018032A1 publication Critical patent/WO1991018032A1/fr

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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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F

Definitions

  • the invention relates to a grafted ethylene vinyl silane copolymer.
  • a compatibilisizer may be incorporated. It can be a block copolymer (e.g. A-B or A-B-A), in which the blocks are comprised of the same monomers as the two homopolymers.
  • the compatibilisizer can also be a grafted copolymer, in which the main polymer and the grafted polymer are the same as the two homopolymers.
  • one of the two copolymers to be joined to each other is prepared in the vicinity of the other polymer by means of a free radical polymerization technique, whereby the polymerizing monomer, from which the polymer is prepared, is grafted on the completed other polymer.
  • This graft copolymer can then be used as such and formed into different articles or be used as a com ⁇ patibilisizer, as mentioned above.
  • the grafting is generally performed by means of a free radical mechanism.
  • a novel feature of this invention is that the grafting is achieved in a new way.
  • This inventive grafted ethylene vinyl silane copolymer is mainly characterized in that it is an etherification product containing an ethylene vinyl silane copolymer and an organic polymer or a copolymer with hydroxy groups.
  • the first embodiment of the method according to the invention is mainly characterized in that an ethylene vinyl silane copolymer is trans-etherified with a polymer or a copolymer containing hydroxy groups.
  • the other embodiment of the method according to the invention is mainly characterized in that an ethylene vinyl silane copolymer is etherified with an unsaturated monomer containing one or more hydroxy groups, whereafter the hydroxy monomer is polymerized or alternatively copolymerized with other monomers containing one or more double bonds, whereby a large number of polymers can be grafted on the ethylene vinyl silane copolymer, whereby, the only requirement for the other monomers concerned is that they can be copoly- ⁇ merized with the hydroxy monomer.
  • the grafting is also achieved by means of trans-etherification.
  • the grafting thus occurs by means of trans-etherificat- ion between the silane group in the polyethylene vinyl silane and some hydroxy monomer, in which case the hydroxy monomer can be grafted as such in the form of a monomer, after which it is polymerized and/or copolymerized with some other monomer containing double bonds.
  • the hydroxy monomer can alternatively be polymerized and/or copolymerized before the grafting with some other monomer and the grafting of this polymer on the polyethylene vinyl silane is then performed in a molten state e.g. in an extruder.
  • graft copolymers according to this application can be used as such and formed into different articles or a compatibilisizer for incompatible polymers.
  • both ways are based on the fact that the grafting itself occurs by means of trans-etherification between the silane group in the poly ⁇ ethylene silane and a hydroxy monomer.
  • a large number of different polymers can be grafted by means of both methods.
  • the only requirement for the fact that it is possible to graft a certain polymer on the polyethylene vinyl silane is that the monomers of the polymer concerned can be copolymerized with the hydroxy monomer, via which the grafting occurs.
  • Useful polymer grades include ethylene polymers, in which the comonomer is a vinyl alkoxy silane compound, e.g.
  • the ethylene copolymer can also include other such comonomers, which can be copolymerized with ethylene, e.g. ⁇ -olefines, such as propylene, butene or hexene, vinyl acetate, C,- -alkyl acrylates and C ⁇ -alkyl methacrylates.
  • ⁇ -olefines such as propylene, butene or hexene, vinyl acetate, C,- -alkyl acrylates and C ⁇ -alkyl methacrylates.
  • the hydroxy monomer is a monomer with one or more double bonds and with one or more hydroxy groups.
  • Suitable hydroxy monomers include e.g. hydroxy alkyl acrylates and methacrylates, allyl alcohol, acrylic and methacrylic acids. Said hydroxy monomers can be used as such or in mixtures with each other.
  • the quantity of the hydroxy monomer of the entire quantity of monomers can be 0.01 - 100% by weight.
  • the hydroxy monomer can be the only monomer, which is incorpoted into the polyethylene silane, but the hydroxy monomer can preferably be copolymerized with some other monomer.
  • This monomer can be any monomer containing double bonds, which can be polymerized by means of a free radical polymerizat ⁇ ion technique.
  • suitable monomers are aromatic vinyl monomers of type styrene and substituted styrenes, such as methyl styrene, isopropylene styrene and ⁇ -methyl styrene.
  • Suitable monomers include acrylonitrile and methacrylonitrile, C 1 -C 7 -alkyl acrylates and methacrylates, acrylic acids and methacrylic acids, vinyl halides, maleic acid anhydride, acrylic amide and methacrylic amide as well as ⁇ -olefines.
  • the monomers can be used as such or in mixtures with each other or together with the hydroxy monomer.
  • the quantity of the "other monomer" of the total quantity of the monomer can be 99.9 - 0 % by weight.
  • the trans-etherification reaction between the hydroxy monomer and the alkoxy vinyl silane can in certain cases occur spontaneously at an elevated temperature.
  • Catalysts can be added in small quantities for speeding up the reaction.
  • catalysts can be used e.g. alkali metal acetates, various acids, e.g. benzoic acid, as well as alkoxides of polyvalent elements M(OR) n , wherein M is preferably Al, Ti or Zr. It is evident for evebody well acquainted with polymer chemistry that grafted products according to the invention can also be achieved in such a way that the silane group and the hydroxy group change places so that the hydroxy group is contained in the ethylene copolymer and the silane group is contained in the other polymer.
  • the hydroxy monomer is first grafted on silane and then polymerized. This can in practise be performed in many different ways.
  • the polymerization can be performed in bulk or in a solution by dissolving the ethylene vinyl silane copolymer in the hydroxy monomer, the "other monomer” and eventually a solvent.
  • the weight ratio between the ethylene vinyl silane copolymer and the grafted polymer can be varied within certain limits by adjusting the viscosity of the mixture with the quantity of the solvent.
  • the polymerization can also be performed by means of a suspension technique. Also in this case the ethylene vinyl silane copolymer is dissolved in the hydroxy monomer and the "other monomer", but no solvent is present. After the grafting of the hydroxy monomer is completed, water and a suspension medium are added and the temperature is increased for polymerizing the monomers. In connection with this method, the maximum quantity of the ethylene vinyl silane copolymer in the final graft copolymer is ca. 30% by weight.
  • a third way for preparing the graft copolymer according to the preparation method I is based on the fact that the ethylene vinyl silane copolymer is main ⁇ tained in a particle form during the polymerization. This facilitates the further handling of the material as well as washing and drying, and no pelletization of the product is needed.
  • This preparation method is described below in detail. Ethylene vinyl silane copolymer particles, the hydroxy monomer and possibly some other monomer, an initiator and possibly a catalyst are mixed at room temperature or at an elevated temperature, but yet at so low a temperature that no polymerization occurs, whereby the particles are impregnated by the mono- mers, the catalyst and the initiators.
  • the particles swell to some extent, but they still maintain their particle structure.
  • the impregnation is most preferably performed in the absence of water for preventing the ethylene vinyl silane copolymer from cross-linking with itself.
  • the ratio between the quantity of the ethylene vinyl silane copolymer and the total quantity of the monomer can be 100 - 0.67.
  • the impregnation can also be performed so that the total quantity of the hydroxy monomer but only part or no quantity of the "other monomer” is added before the impregnation phase.
  • the remaining quantity of the "other monomer” is added after the water suspension has been prepared.
  • the monomer can be added at the same time or in drops during several hours.
  • the impregnation phase can be extended by using grafting instead of cross- linking so that the monomers, the catalyst and the initiators can be totally impregnated before water and the suspension medium are added.
  • the temperature is increased, wereby the grafted hydroxy monomer as well as the free monomer are polymerized, after which grafted polymer chains are formed on the ethylene vinyl silane copolymer.
  • the polymer particles are washed and dried.
  • Such substances can be used as the suspension medium, which are conven ⁇ tionally used in connection with suspension polymerization of vinyl monomers.
  • These include e.g. water soluble polymers, such as polyvinyl alcohol, polyvinyl pyrrolidone and methyl cellulose or partially water soluble substances, such as calcium triphostate and magnesium pyrophostate.
  • the initiator has to be oil soluble, since the polymerization is performed by means of water suspension technique, and it has to have a half-time of 10 hours within a temperature range of 50-140°C.
  • Initiators which can be used for polymerizing the vinyl monomer, include organic peroxides, such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, dikumyl peroxide as well azo compounds, such as azobisisobutyronitrile and azobisdimethyl valeronitrile. More than one initiator are preferably used simultaneously so that the polymerization is started at a low temperature with a low temperature initiator and completed at a high temperature with a high temperature initiator.
  • the total quantity of the initiator can be 0.01 - 4 weight fractions and most preferably 0.1 - 0.2 weight fractions, based on 100 weights fractions of the monomer.
  • Fig. 1 is illustrated the preparation method I.
  • an ethylene vinyl trimethoxy silane copolymer which is grafted with hydroxy ethyl methacrylate during the release of methanol and after the subsequent copoly- merization with styrene.
  • the hydroxy monomer is first polymeriz ⁇ ed either as a homopolymer or a copolymer with one or more other monomers. This polymer is then admixed with an ethylene vinyl silane copolymer as well as a catalyst e.g. in an extruder, whereby the hydroxy monomer containing the polymer is grafted via a trans-etherification reaction.
  • the advancement of the reaction is illustrated in Fig. 2, in which a copolymer of styren and hydroxy ethyl methacrylate is grafted on ethylene vinyl trimethoxy silane during the release of methanol.
  • the grafting is thus achieved by blending two polymers in an extruder. It is therefore not important, how the hydroxy mono ⁇ mer containing the polymer has been prepared, but the main point is that it has reactive hydroxy groups.
  • the preparation method for the polymer containing the hydroxy monomer can be free radical polymerization in bulk, in a solution or suspension, depending on the monomers to be used.
  • the two polymers can be blended in any ratio with respect to each other.
  • the two polymers can be made to react with each other by means of so-called reactive film coextrusion. In this case, a good adhesion is achieved between the two films without having to use an adhesive medium.
  • Typical applications for these materials include their use as compabilitisizers, adhesive plaster or as a polymer component in rubber bitumen.
  • the basic material can also be blended or impregnated with a foaming agent and foamed into elastic foam plasters.
  • the polymer can be handled with known methods designed for thermoplaster, e.g. extrusion, injection moulding, press forming, film blowing, extrusion coating.
  • a 2-liter reactor was filled with 100 weight fractions of Visico 1407 (a commer ⁇ cial ethylene butyl acrylate vinyl trimethoxy silane terpolymer) in a particle form, the particle diameter being 3-4 mm, 36 weight fractions of styrene, 4.9 weight fractions of hydroxy ethyl methacrylate as well as 0.14 weight fractions of ben ⁇ zoyl peroxide as an initiator.
  • This mixture was agitated slowly, 60 rpm, tead the temperature was increased to 75°C and was maintained there for three hours to allow the monomers and the initiator to diffuse in the Visico particles and to allow the hydroxy ethylene methacrylate to graft on the Visico polymer chains.
  • a water suspension was prepared by adding 435 weight fractions (882 g) of water and, as suspension media, 1.0 weight fractions of tricalciumphostate and 0.02 weight fractions of potassium dodecyl benzene sulphonate. The temperature was then increased to 90°C and the remaining quantity of styrene, 64 weight fractions, (the total quantity of styrene 100 weight fractions) containing 0.26 weight fractions of benzoyl peroxide and 0.67 weight fractions of tert-butyl perbenzoate were added in drops during 4.5 hours. The polymerization was completed at 125°C for 4 hours. The polymerization product was in the form of separate homogenous particles.
  • This example was realized according to Example I, 1, except that also 0.01 weight fractions of benzoic acid were added as a catalyst with the first batch of the monomer for the grafting reaction.
  • This example was realized according to Example I, 1, except that 1.0 weight fractions of titan tert-butoxide was added as a catalyst with the first batch of the monomer and that the quantity of hydroxy ethyl metacrylate was 10 weight fractions.
  • Table 1 lists the results of extraction tests and DSC runs of products of Examp ⁇ les I, 1 - 1, 4. The table shows that the share of insoluble matter increases when the catalyst concentration increases at the same time as the share of Visico in the insoluble gel decreases, which indicates that the grafting has occurred.
  • a 2-liter reactor was filled with 100 weight fractions of styrene, 5.4 weight fractions of hydroxy ethyl methacrylate, 246 weight fractions of water (980 g), as well as as initiators,with 0.63 weight fractions of benzoyl peroxide and 0.21 weight fractions of tert-butyl perbenzoate.
  • the polymerization was realized by means of a suspension technique in a conventional polystyrene related manner, and gelatine and bentonite were used as suspension media. The polymerization was performed at 95°C and 135°C during altogether 8 hours.
  • the molar weight of the product was M w 110000 and dispersity 2.8.
  • Example 2 was performed in accordance with Example II, 2 except that 0.3 weight fractions of benzoic acid were added as a catalyst during agitation in the extruder.
  • the trans-etherification reaction between the hydroxy group in the hydroxy ethyl methacrylate styrene copolymer and the silane group in the Visico polymer is in this case more effective than in Example II, 2 and the share of soluble matter in methyl ethylene ketone ⁇ 1.0%.
  • Example 2 was performed in accordance with Example II, 2 except that 0.3 weight fractions of trinonyl phenyl phosphite were added as a catalyst during agitation in the extruder. When this material was stretched by 500% and then allowed to shrink, the remaining stretch was 400%, which indicates that the material has elastomeric properties.

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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)
  • Graft Or Block Polymers (AREA)

Abstract

Pour améliorer la miscibilité de deux polymères habituellement non miscibles et pour empêcher une séparation de phase complète pendant leur manipulation, l'un des deux polymères peut être greffé sur l'autre. A cet effet, on éthérifie un polymère d'éthylène/silane de vinyle contenant des groupes méthoxy avec un autre polymère contenant des groupes hydroxy ou avec un monomère contenant des groupes hydroxy. Par exemple, en mélangeant le copolymère de méthacrylate d'hydroxyéthyle et de styrène avec le terpolymère d'acrylate d'éthyle et butyle et de silane triméthoxy de vinyle, on amène le copolymère à se greffer avec le terpolymère de silane par éthérification des groupes hydroxy et des groupes méthoxy. Dans une variante, le méthacrylate d'hydroxyéthyle et de styrène peut être mélangé avec un terpolymère de silane, d'abord par éthérification des groupes hydroxy du monomère de méthacrylate et des groupes méthoxy du terpolymère, puis par copolymérisation du styrène avec du méthacrylate d'hydroxyéthyle. Le produit qui en résulte est très homogène et peut être utilisé comme agent de compatibilité, comme plastique adhésif et comme composant polymère dans des bitumes à base de caoutchouc.
PCT/FI1991/000099 1990-05-18 1991-04-05 Copolymere d'ethylene/silane de vinyle et preparation de ce compose WO1991018032A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP91506904A JPH05507098A (ja) 1990-05-18 1991-04-05 エチレンビニルシラン共重合体及びその製造

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI902479A FI902479A (fi) 1990-05-18 1990-05-18 Eten-vinylsilansampolymer och dess framstaellning.
FI902479 1990-05-18

Publications (1)

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WO1991018032A1 true WO1991018032A1 (fr) 1991-11-28

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JP (1) JPH05507098A (fr)
FI (1) FI902479A (fr)
WO (1) WO1991018032A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2699186A1 (fr) * 1992-12-14 1994-06-17 Total Raffinage Distribution Compositions bitume-polymère, leur procédé de préparation et leurs applications.
US5703148A (en) * 1993-09-09 1997-12-30 Total Raffinage Distribution S.A. Asphalt-polymer compositions, process for making same and uses thereof
WO2012032005A1 (fr) * 2010-09-07 2012-03-15 Basf Se Terpolymère à base d'oléfines déficitaires en électrons, d'oléfines sans substituants accepteurs d'électrons et d'alcoxyvinylsilanes
KR20140007843A (ko) * 2011-01-18 2014-01-20 바스프 에스이 가수분해-안정성 폴리아미드
CN112011315A (zh) * 2020-09-14 2020-12-01 中国石油大学(华东) 一种抗超高温油基钻井液用无机/聚合物复合材料封堵剂及其制备方法与应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0183493A2 (fr) * 1984-11-22 1986-06-04 Mitsui Petrochemical Industries, Ltd. Copolymère statistique modifié d'ethylène
SE458928B (sv) * 1984-02-03 1989-05-22 Neste Oy Med alkoxisilan modifierad polyolefin med goda vidhaeftningsegenskaper
WO1991004995A1 (fr) * 1989-10-03 1991-04-18 Exxon Chemical Patents Inc. Copolymeres greffes thermoplastiques et leur emploi comme agents de compatibilite

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE458928B (sv) * 1984-02-03 1989-05-22 Neste Oy Med alkoxisilan modifierad polyolefin med goda vidhaeftningsegenskaper
EP0183493A2 (fr) * 1984-11-22 1986-06-04 Mitsui Petrochemical Industries, Ltd. Copolymère statistique modifié d'ethylène
US4908411A (en) * 1984-11-22 1990-03-13 Mitsui Petrochemical Industries, Ltd. Modified ethylenic random copolymer
WO1991004995A1 (fr) * 1989-10-03 1991-04-18 Exxon Chemical Patents Inc. Copolymeres greffes thermoplastiques et leur emploi comme agents de compatibilite

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2699186A1 (fr) * 1992-12-14 1994-06-17 Total Raffinage Distribution Compositions bitume-polymère, leur procédé de préparation et leurs applications.
EP0603028A1 (fr) * 1992-12-14 1994-06-22 Total Raffinage Distribution S.A. Compositions bitume-polymère, leur procédé de préparation et leurs applications
US5428085A (en) * 1992-12-14 1995-06-27 Total Raffinage Distribution Sa Bitumen-polymer compositions, their method of preparation and their uses
US5703148A (en) * 1993-09-09 1997-12-30 Total Raffinage Distribution S.A. Asphalt-polymer compositions, process for making same and uses thereof
WO2012032005A1 (fr) * 2010-09-07 2012-03-15 Basf Se Terpolymère à base d'oléfines déficitaires en électrons, d'oléfines sans substituants accepteurs d'électrons et d'alcoxyvinylsilanes
CN103189401A (zh) * 2010-09-07 2013-07-03 巴斯夫欧洲公司 从缺电子烯烃、不含吸电子取代基的烯烃和烷氧基乙烯基硅烷形成的三元共聚物
KR101781668B1 (ko) 2010-09-07 2017-10-23 바스프 에스이 전자-부족 올레핀, 전자-끄는 치환기를 갖지 않는 올레핀 및 알콕시비닐실란으로부터 형성된 삼원공중합체
KR20140007843A (ko) * 2011-01-18 2014-01-20 바스프 에스이 가수분해-안정성 폴리아미드
KR101869999B1 (ko) 2011-01-18 2018-06-22 바스프 에스이 가수분해-안정성 폴리아미드
CN112011315A (zh) * 2020-09-14 2020-12-01 中国石油大学(华东) 一种抗超高温油基钻井液用无机/聚合物复合材料封堵剂及其制备方法与应用
CN112011315B (zh) * 2020-09-14 2021-05-28 中国石油大学(华东) 一种抗超高温油基钻井液用无机/聚合物复合材料封堵剂及其制备方法与应用

Also Published As

Publication number Publication date
EP0528806A1 (fr) 1993-03-03
JPH05507098A (ja) 1993-10-14
FI902479A (fi) 1991-11-19
FI902479A0 (fi) 1990-05-18

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