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EP0986591A1 - Procede de preparation de copolymeres pour revetements polymeres antistatiques - Google Patents

Procede de preparation de copolymeres pour revetements polymeres antistatiques

Info

Publication number
EP0986591A1
EP0986591A1 EP98924348A EP98924348A EP0986591A1 EP 0986591 A1 EP0986591 A1 EP 0986591A1 EP 98924348 A EP98924348 A EP 98924348A EP 98924348 A EP98924348 A EP 98924348A EP 0986591 A1 EP0986591 A1 EP 0986591A1
Authority
EP
European Patent Office
Prior art keywords
stage
monomers
latex
methacrylic acid
copolymerization
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.)
Withdrawn
Application number
EP98924348A
Other languages
German (de)
English (en)
Inventor
Oleg Nikolaevich Primachenko
Valery N. Pavlyuchenko
Klavdia A. Gagarina
Sergey Stepanovich Ivanchev
Mikael Skrifvars
Hanna Laamanen
Jukka Koskinen
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.)
Neste Chemicals Oy
Original Assignee
Neste Chemicals 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 Chemicals Oy filed Critical Neste Chemicals Oy
Publication of EP0986591A1 publication Critical patent/EP0986591A1/fr
Withdrawn legal-status Critical Current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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes

Definitions

  • the present invention is related to a method for the preparation of copolymers by latex copolymerization for antistatic polymeric coatings.
  • copolymers can be used as antistatic and electric dissipative materials, as coatings in pulp and paper industry, in ship building industry, in electronic industry and also for the manufacture of photographic materials and instruments.
  • the patent publication CN 1084200 describes the preparation and use of antistatic coatings based on polymeric compounds in the latex form, and specially some styrene-acrylate latex compounds with low molecular antistatic agents, fillers and pigments are disclosed.
  • the latex copolymers of this publication are used as binders for antistatic agents, fillers and pigments.
  • Low molecular antistatic agents are not able to provide coatings with a stable long- term antistatic effect due to the antistatic diffusion from the surface of the coating.
  • Another disadvantage of the disclosed latex compounds is the fact that when various ingredients are added to the latex, problems appear with the aggregative stability of the latex compound and its long-term storage stability, when segregation and separation tend to occur.
  • EP 338 486 is disclosed a process for the production of stable emulsion polymers with inverted core-shell latex particle structure suitable for the production of functionalized latexes. At the first stage of the process low molecular hydrophilic copolymer in latex form is formed. At this stage it is possible to produce amine and carboxy containing latexes.
  • the hydrophobic core of the latex particle is formed in the presence of the hydrophilic copolymer latex.
  • This process requires the use of 0.5—6% of chain transfer agent, and water soluble initiators of persulphate type to obtain low molecular hydrophilic copolymer.
  • chain transfer agent 0.5—6%
  • water soluble initiators of persulphate type to obtain low molecular hydrophilic copolymer.
  • bromine containing compounds as chain transfer agents in such high concentrations as described in this publication may result in undesireable colouring of the coatings and thus it limits the applications of these latexes.
  • the distribution is a very important parameter for the formation of latex coatings with antistatic properties, in this process the functionalized copolymer is concentrated on the surface of the latex particle.
  • An object of the present invention lies in providing a method for the preparation of stable copolymers for antistatic latex coatings characterized by high water resistance and good adhesion to various supports.
  • a further object lies in developing of processes for the production of copolymer latexes for antistatic polymeric coatings with improved antistatic properties and higher water resistance.
  • a further object lies in providing a method for the manufacture of concentrated latexes with solid content exceeding 40 % and with low viscosity.
  • the process according to the invention for the manufacture of antistatic copolymer latexes based on vinyl aromatic compounds, alkyl esters of methacrylic acid or acrylic acid and aminealkyl esters of methacrylic acid and/or vinylpyridine derivatives is characterized in that the latexes of the above copolymers are prepared by emulsion copolymerization in the presence of trimethylalkylammonium halogenide in the amount of 2—4% of the total weight of the monomers in combination with a water soluble initiator, wherein the formation of latex particles with the direct morphology of core-shell takes place, the core consisting of the copolymer formed in stage 1 of the process and the shell consisting of the copolymer formed in stage 2 of the process.
  • the inventors of the present invention have been able to develop methods for the production of amine containing copolymers of core-shell type in the form of aqueous latexes with the aid of two stage core-shell emulsion copolymerization in the presence of cationic surfactants in combination with water soluble azo compounds.
  • These methods for the preparation of latex copolymers for antistatic coatings are actually processes for the production of functionalized latexes.
  • the shell of the latex particle contains copolymers with ionizable functional groups, which impart stable antistatic properties to the coatings based on such copolymers. Amine and ammonium groups can be used as such funktional groups of the copolymer.
  • a trimethylammonium halogenide is used as cationic surfactant.
  • the alkyl group is selected from cetyl, dodecyl and stearyl groups.
  • the preferable surfactant is dodecyltrimethylammonium halogenide.
  • Cationic surfactants may act as antistatics, and here cationic surfactans such as trimethylalkylammonium halides are used as emulgators which provide aggregative stable amine containing latexes.
  • the functional groups of said cationic surfactants are compatible with the functionalized copolymers being synthesized, i.e.
  • the seed latexes of copolymers, which form the cores of the latex particle are proucked at the first stage of the process.
  • the seed latexes are based on vinyl aromatic compounds, alkyl esters of methacrylic acid or acrylic acid. Dimethacrylic ester of ethyleneglycol is used as a cross-linking agent with the weight ratio of monomers equal to 20-80:79—19.9: 1.0-0.1, preferably 40-60:59.8—39.6:0.2-0.4 in the case of single feeding of the monomeric mixture to the emulsifier solution.
  • the second stage of the process is the formation of the amine containing shell of the latex particle.
  • the final stage is carried out stepwise with feeding of the monomeric mixture of vinyl aromatic compound, alkyl ester of methacrylic acid or acrylic acid, aminealkyl ester of methacrylic acid and/or vinylpyridine derivative with the weight ratio of monomers equal to 25— 50:65— 15: 10— 35, preferably 33—40:53—22: 14—28 or alternatively with feeding of vinylaromatic compound, alkylester of methacrylic acid or acrylic acid, aminealkyl ester of methacrylic acid and/or vinylpyridine derivative, dimethacrylic ester of ethylenelycol as a cross-linking agent with the weight ratio of monomers equal to 25—50:64—14.9:10—35:0.1—0.1, preferably 36.3—51.6:54—34:9.514:0.2-0.4.
  • the amounts of vinylaromatic compound and alkyl esters of methacrylic acid or acrylic acid can be varied within the range of 20—75 % calculated from the total amount of the monomers, and preferably within the range of 25—50 % .
  • Styrene and alkyl or halogen substituted derivatives of styrene can be used as vinyl- aromatic compounds, preferably styrene and p-methylstyrene are used.
  • Methyl, ethyl, butyl, octyl or 2-ethylhexyl acrylates and methyl, ethyl or butyl methacrylates can be used as alkyl esters of methacrylic acid or acrylic acid and preferably methyl and butyl aery late and butyl methacrylate are used.
  • Dimethyl and diethylamineethyl methacrylates can be used as aminealkyl esters of methacrylic acid.
  • Vinylpyridine, 2-methy 1-5 -vinylpyridine, 5 -ethy 1-2- vinylpyridine, l,2-dimethyl-5- vinylpyridinylmethyl sulphate can be used as derivatives of vinylpyridine, preferably 2-methy 1-5 -vinylpyridine is used.
  • the ratio of monomers and water in the manufacturing process of latexes can vary from 1 : 1 to 1 :4, preferably the ratio 1: 1 to 1:2 is used.
  • the latex copolymerization reaction is carried out at the temperature range of 65—85 °C, preferably at 70-80 °C.
  • the latexes are polymerized at pH of the reaction equal to 1—8, and acidifying reagents, in particular hydrochloric acid may optionally be used.
  • aggregative stable latexes are prepared in both acidic, neutral and weakly alkaline fluids.
  • amine alkyl esters of methacrylic acid DMAEMA and DEAEMA
  • aggregative stable latexes are prepared only in acidic conditions, and in this case it is necessary to use hydrochloric acid.
  • hydrochloric acid is also necessary for the transformation of the functional groups of amine monomers into salt form, and it improves the antistatic properties of coatings based on such copolymers.
  • initiators such as cumene hydroperoxide, /3-oxyethyl-tert-butyl peroxide, -oxypropyl-tert-butyl peroxide and 2,2'-azo-bis-(2-aminepropane) dihydrochloride can be used, as well as chain transfer agents such as tert-dodecyl mercaptane, inor ganic pigments such as titanium dioxide and coalescent additives such as monoethy ester of ethyleneglycol (ethyl cellosolve) can be applied.
  • the functionalized latexes manufactured according to the present method are suitable for the concentrated stable latexes with approximately 50 % or more solids due to the increased particle size of the latex particle formed, due to lower surface energy of the system and due to lower viscosity of the latex.
  • BA 7.0 g (7 % w / w ) diethyl amine ethyl methacrylate (DEAEMA), 0.15 g (0.15 % w / w ) DMEG, which amounts to 75 % of the total weight of monomers, is started and continued for 4 h with the rate of 18.75 g/hr. 2 h after the beginning of the of copolymerization stage 0.1 g (0.1 % w / w ) of the azo initiator is charged. When the feeding of the monomer mixture is completed the last portion of the azo initiator
  • Seed polymerization 2 g (2 % w / w ) TMDDAC Stage 1 30.0 g (30.0 % w / w ) ST
  • Seed polymerization 2.0 (2 % w / w ) TMDDAC Stage 1 16.61 g (16.61 % w / w ) ST 16.61 g (16.61 % w / w ) BA 0.067 g (0.067 % w / w ) DMEG (33.3% of the total weight of the monomers)
  • Seed polymerization 2.0 g (2 % w / w ) TMDDAC Stage 1 37.45 g (37.45 % w / w ) ST
  • Seed polymerization 4.0 g (4 % wt.) TMDDAC Stage 1 29.98 g (29.98 % w / w ) ST
  • Seed polymerization 2.0 g (2 % w / w ) TMDDAC Stage 1 22.45 g (22.45 % w / w ) ST
  • Seed polymerization 4.0 g (4 % w / w ) TMDDAC Stage 1 11.83 g (11.83 % w / w ) ST
  • Seed polymerization 4.0 g (4.0 % w / w ) TMDDAC Stage 1 11.87 g (11.87 % w / w ) ST
  • a procedure according to example 1 by stepwise feeding of TMDD AX (20 % at stage 1, 80 % at stage 2), with the exceptions that the amount of hydrochloric acid added in the beginning of the copolymerization stage was 6.0 ml and temperature was finally raised to 80 °C, was performed with the following amounts of starting materials: Seed polymerization: 0.8 g (0.8 % w/w) TMDDAC Stage 1 11,83 g (11.83 % w/w) ST
  • Seed copolymerization is carried out at 80°C for 0.5 h. Then the monomer mixture consisting of 12.8 g ST, 8.56 g BA and 5.34 DEAEMA amounting to 26.66 % of the total weight of comonomers is fed into the seed latex as well as 0.8 g T-DDM at 80 °C for 0.5 h with the feeding rate of 55 g/h. During the feeding of the monomer mixture the temperature of the seed latex is maintained at 80 °C for 1 h. Then the amine groups of the seed latex are neutralized by feeding 11.6 ml 5 % HCI aqueous solution to the latex at 80 °C for 0.5 h.
  • the monomer mixture consisting of 12.8 g (12.8 % w / w ) ST, 8.54 g (8.54 % w / w ) BA and 5.34 g (5.34 % w / w ) DEAEMA amounting to 26.68 % of the total weight of comonomers and 0.8 g (0.8 % w / w ) T-DDM is fed into the reaction mixture with the rate of 54.96 g/h.
  • the reaction mixture is kept at 80 °C for 1 h.
  • stage I the latex is neutralized with 11.6 ml of 5% aqueous solution of hydrochloric acid during 0.5 h.
  • stage 2 0.5 g (0.5 % / w ) azo initiator is fed into the latex and the monomer mixture consisting of 33.33 g (33.33 % w / w ) ST, 13.33 g (13.33 % w / w ) BA and 20 g (20 % w / w ) butyl methacrylate (BMA) amounting to 66.66 % of the total weight of comonomers, is charged for 1 h with the rate of 66.7 g/h.
  • the latex is kept at 80 °C for 1 h.
  • stage 2 25 % of the amine groups are neutralized with 3.9 ml of 5 % aqueous solution HCI for 0.5 h.
  • the obtained latex is kept at 80 °C for 0.5 h, cooled and collected.
  • the monomer/ water ratio is 1:2.

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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)

Abstract

L'invention concerne un procédé de préparation de copolymères par copolymérisation au latex pour revêtements polymères antistatiques consistant à fabriquer des latex copolymères antistatiques à base de composés vinyliques aromatiques, d'alkylesters d'acide méthacrylique ou d'acide acrylique et d'amine-alkylesters d'acide méthacrylique et/ou de dérivés de vinylpyridine. Les latex des copolymères susmentionnés sont préparés par copolymérisation par émulsion en présence d'halogénure d'ammonium d'alkyle triméthylé dans une proportion comprise entre 2 et 4 % du poids total des monomères en combinaison avec un initiateur hydrosoluble. La formation des particules de latex présente la structure directe du type noyau-enveloppe, le noyau comprenant le copolymère formé à l'étape 1 du procédé et l'enveloppe comprenant le copolymère formé à l'étape 2 du procédé.
EP98924348A 1997-06-05 1998-06-03 Procede de preparation de copolymeres pour revetements polymeres antistatiques Withdrawn EP0986591A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI972381 1997-06-05
FI972381A FI972381A7 (fi) 1997-06-05 1997-06-05 Menetelmä kopolymeerien valmistamiseksi antistaattisia polymeeripinnoitteita varten
PCT/FI1998/000480 WO1998055522A1 (fr) 1997-06-05 1998-06-03 Procede de preparation de copolymeres pour revetements polymeres antistatiques

Publications (1)

Publication Number Publication Date
EP0986591A1 true EP0986591A1 (fr) 2000-03-22

Family

ID=8548990

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98924348A Withdrawn EP0986591A1 (fr) 1997-06-05 1998-06-03 Procede de preparation de copolymeres pour revetements polymeres antistatiques

Country Status (4)

Country Link
EP (1) EP0986591A1 (fr)
AU (1) AU7657498A (fr)
FI (1) FI972381A7 (fr)
WO (1) WO1998055522A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI991051L (fi) * 1999-05-07 2000-11-08 Neste Chemicals Oy Huokosia sisältävien polymeerihiukkasten valmistamismenetelmä
FI991050A7 (fi) * 1999-05-07 2000-11-08 Neste Chemicals Oy Lateksikoostumukset ja niiden valmistamismenetelmä
US6885699B2 (en) 2000-07-24 2005-04-26 Stmicroelectronics Ltd. Semi-stationary quiescent mode transmission
WO2021228895A1 (fr) 2020-05-11 2021-11-18 Eurovia Émulsions de liant hydrocarboné modifiées par latex cationique et leur utilisation dans la préparation de produits bitumineux

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8916944D0 (en) * 1989-07-25 1989-09-13 Ici Plc Composite particle dispersions
US5306776A (en) * 1992-05-06 1994-04-26 Sumitomo Chemical Company, Limited Multilayered polymer
US5604076A (en) * 1996-02-01 1997-02-18 Xerox Corporation Toner compositions and processes thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9855522A1 *

Also Published As

Publication number Publication date
FI972381L (fi) 1998-12-06
FI972381A7 (fi) 1998-12-06
WO1998055522A1 (fr) 1998-12-10
FI972381A0 (fi) 1997-06-05
AU7657498A (en) 1998-12-21

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