EP0914358A1 - Thermoformable cast poly(methyl methacrylate) - Google Patents

Thermoformable cast poly(methyl methacrylate)

Info

Publication number
EP0914358A1
EP0914358A1 EP97933765A EP97933765A EP0914358A1 EP 0914358 A1 EP0914358 A1 EP 0914358A1 EP 97933765 A EP97933765 A EP 97933765A EP 97933765 A EP97933765 A EP 97933765A EP 0914358 A1 EP0914358 A1 EP 0914358A1
Authority
EP
European Patent Office
Prior art keywords
methacrylate
poly
weight
curable composition
sheet
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Withdrawn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
EP97933765A
Other languages
German (de)
French (fr)
Inventor
John Patrick Lynch
Derek John Irvine
Gordon Maxwell Beverly
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.)
Mitsubishi Chemical UK Ltd
Original Assignee
Imperial Chemical Industries Ltd
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 Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of EP0914358A1 publication Critical patent/EP0914358A1/en
Withdrawn legal-status Critical Current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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof

Definitions

  • thermoformable cast poly(methyl methacrylate) is prepared by polymerising suitable curable compositions between sheets of glass (cell casting) or between two opposing endless metal bands (band casting) so as to provide the thermoformable cast poly(methyl methacrylate) in the form of sheet.
  • T e sheet can be subsequently thermoformed to manufacture articles such as sanitary ware, e.g. baths, washbasins and shower trays.
  • the sheet is preheated to a predetermined temperature, for example as calculated according to the formula stated in GB 1577517, and is then drawn into a mould under the influence of pressure or vacuum.
  • the present invention is directed towards an improved thermoformable cast poly(methacrylate), such as poly(methyl methacrylate), particularly in the form of sheet, which does not need to be thermoformed at relatively high temperatures, which has acceptable Vicat
  • the present invention provides a curable composition capable of being cured to form a thermoformable cast poly(methacrylate) which composition comprises
  • thermoformable cast poly(methacrylate) sheet capable of being formed from a curable composition as hereinbefore
  • TGA thermogravimet ⁇ c analysis
  • the poly(methacrylate) in the syrup is preferably formed from the same monomeric methacrylate which is also present in the syrup.
  • the poly(methacrylate) represents from 5 to 35 %, more typically from 5 to 15 %, by weight of the syrup and preferably from 7 to
  • the syrup may be prepared by the mixing of the poly(methacrylate) with the monomeric methacrylate, it is preferred that the syrup is prepared by partially polymerising the monomeric methacrylate so as to form the poly(methacrylate) in situ The conditions are controlled such that the poly(methacrylate) formed in situ is of an appropriate molecular weight for use in the
  • the poly(methyacrylate) and monomeric methacrylate are preferably derived from lower alkyl methacrylates, e.g. C, to C 4 methacrylates, and in particular methyl methacrylate
  • the poly(methacrylate) may be a copolymer Additionally, one or more monomeric methacrylates may be used.
  • the poly(methacrylate) is a homopolymer, particularly poly(methyl methacrylate) and that the monomeric methacrylate is methyl methacrylate.
  • the use of the catalytic chain transfer agent allows for the incorporation of a minor proportion of one or more lower alkyl acrylates, C, to C 4 acrylates, into the curable
  • the acrylate is butyl acrylate
  • the at least one initiator may be one or more initiators commonly used in the preparation of conventional thermoformable cast poly(methacrylate) Suitable initiators include azodnsobutyronitrile, peroxydicarbonates such as di-isopropyl, di-n-butyl, di-isobutyl, 5 dicyclohexyl, or b ⁇ s-(4-t-butyl cyclohexyl) peroxydicarbonate, and t-butyl perpivalate
  • two or more initiators are chosen such that the lifetime and activity of the initiators are optimised during curing.
  • the catalytic chain transfer agent, or residue thereof, is or is derived from a cobalt chelate
  • Suitable cobalt chelates are as described in US 4694054, US 5028677 and US 10 4680352 Particularly preferred is a cobalt chelate having the following general formula I
  • R can be selected from of a variety of groups such as methyl and phenyl, particularly phenyl, and which is known generally as CoBF.
  • the catalytic chain transfer agent is or is derived from cobaloxime.
  • the catalytic chain transfer agent is added at very low concentrations, i e. from 0.0001 to 0.001 , for example from 0.001 to 0.0005, % by weight on the curable composition 5
  • the catalytic chain transfer agent is present from 0 00025 to 0.0003 % by weight, i e 2 5 to 3 ppm, in the curable composition
  • the average molecular weight is in the range 350000 to 500000 and in particular from 380000 to 480000.
  • Increased amounts of the catalytic chain transfer agent reduce the molecular weight.
  • thermoformable cast poly(methacrylate) of the present invention shows some decomposition between 260 and 300°C typical of non-saturated terminal groups.
  • the poly(methacryiate) is formed in situ by the use of a catalytic chain transfer agent as hereinbefore described the syrup will contain residues of such a chain transfer agent. Such residues will be present in the syrup at the levels hereinbefore stated.
  • the crosslinking agent may be chosen from any conventionally used.
  • the crosslinking agent is chosen from at least one of ethylene glycol dimethacrytate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, triallyl cyanurate, allyl methacrylate, allyl acrylate, triallyl phosphate, diallyl maleate, methallyl acrylate, vinyl methacrylate and divinyl benzene.
  • ethylene glycol dimethacrylate Particularly preferred is ethylene glycol dimethacrylate.
  • Other conventional additives include splitting aids such as Texol (obtained from
  • Example 1 illustrates the present invention.
  • a reactive mixture was prepared containing 2000 kg of monomeric methyl methacrylate, 100 g of UV stabiliser (Aduvex - The Great Lakes Fine Chemicals Ine), 1200 g of splitting aid (Texol) and 38 g of initiator (azodiisobutyronitrile - AZDN). The mixture was stirred and heated to about 82°C until a syrup containing about 8% by weight of poly(methyl methacrylate) was formed.
  • UV stabiliser Aduvex - The Great Lakes Fine Chemicals Ine
  • Texol splitting aid
  • initiator azodiisobutyronitrile - AZDN
  • a curable composition was formed having the following composition:
  • the curable composition was stirred and then poured into casting cells formed from sheets of glass so as to eventually provide sheets having thicknesses of 3.2 and 5 mm respectively. Curing followed a two stage heating process. The filled cells were first slowly heated to 90 D C at which they were held for 1 hour. Thereafter the temperature was slowly raised to about 120 C C at which they were held for a further 30 minutes. After curing, the cells were slowly cooled to room temperature.
  • the 5 mm thick sheets had a Vicat Softening Point (VSP) of 107.4°C and the 3 mm thick sheets had a VSP of 108.0°C.
  • VSP Vicat Softening Point
  • TGA of samples of the sheet showed decomposition occurring between 260 and
  • thermoformable cast poly(methacryiate) prepared in the absence of cobalt chelate 300°C which was absent from conventional thermoformable cast poly(methacryiate) prepared in the absence of cobalt chelate.
  • Example 1 was repeated except that the CoBF was replaced by cobaloxime.
  • the 5mm sheet had a VSP of 109.2°C and showed a decomposition between 260 and 300 C C when subjected to TGA.
  • Example 2 was repeated except that the cobaloxime was used at a level of 3ppm.
  • the 5mm sheet had a VSP of 109.6°C and again showed decomposition between 260 and 5 300°C.
  • Example 1 was repeated except that the syrup contained 3.4 % by weight of butyl acrylate.
  • the 3.2 mm sheet had a VSP of 105.4°C and the 5 mm sheet had a VSP of 105.2°C

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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

A curable composition capable of being cured to form a thermoformable cast poly(methacrylate) comprising at least from 95 % by weight of a syrup which is a solution of a poly(methacrylate) in a curable monomeric methacrylate, from 0.05 to 0.1 % by weight of at least one initiator capable of initiating the curing of the curable monomeric methacrylate, from 0.0001 to 0.0005 % by weight of a catalytic chain transfer agent which is or which is derived from a cobalt chelate, from 0.05 to 0.1 % by weight of a cross-linking agent; and optionally one or more of conventional additives selected from splitting aids, pigments, peak suppressors and stabilisers. A thermoformable sheet formed from such a composition and a thermoformed article produced from such a sheet. The thermoformable sheet does not need to be thermoformed at relatively high temperatures, has an acceptable Vicat Softening Point, does not emit unpleasant odours on heating and meets stringent industry standards.

Description

Thermoformable Cast Poly(methyl methacrylate)
The present invention relates to thermoformable cast poly(methyl methacrylate). Conventionally, as described in US 4113803, thermoformable cast poly(methyl methacrylate) is prepared by polymerising suitable curable compositions between sheets of glass (cell casting) or between two opposing endless metal bands (band casting) so as to provide the thermoformable cast poly(methyl methacrylate) in the form of sheet.
T e sheet can be subsequently thermoformed to manufacture articles such as sanitary ware, e.g. baths, washbasins and shower trays. In the thermoforming process, the sheet is preheated to a predetermined temperature, for example as calculated according to the formula stated in GB 1577517, and is then drawn into a mould under the influence of pressure or vacuum.
Problems associated with the thermoforming of such sheet are discussed in US 4113803, in particular the difficulty of forming complex shaped articles and the conflict between increasing the rate at which the articles are formed by raising the thermoforming temperature and the risk of thermal degradation at such higher temperatures. US 4113803 states that the prior art solutions to the above problems of including a plasticiser into the curable composition or to ensure that the poly(methyl methacrylate) is of a sufficiently low molecular weight result in a deterioration of mechanical and haze resistance properties of a thermoformed article. US 4113803 proposes a further solution in which a small amount of cross-linking agent is added to the curable composition which has a reduced viscosity as therein defined of between 1.5 and 4.0. Unfortunately, the sheet produced according to US 4113803 still has to thermoformed at relatively high temperatures thereby increasing the time it takes to produce an article.
Alternatively, current commercially available sheet contains a small percentage of lower alkyl acrylate, e.g. butyl acrylate, in order to allow the sheet to be thermoformed at lower temperatures. Unfortunately, such sheet has, according to certain industry standards, an unacceptably low Vicat Softening Point and thereby is unsuitable for use in sanitary ware.
Further alternatives wherein the molecular weight and polydispersivity of the poly(methyl methacrylate) is controlled by the use of mercaptan based chain transfer agents results in sheets which have good thermoformability but poor performance in the standard heat tests and also emit unpleasant odours on heating.
The present invention is directed towards an improved thermoformable cast poly(methacrylate), such as poly(methyl methacrylate), particularly in the form of sheet, which does not need to be thermoformed at relatively high temperatures, which has acceptable Vicat
Softening Point, which does not emit unpleasant odours on heating and which meets stringent industry standards. Accordingly in a first aspect the present invention provides a curable composition capable of being cured to form a thermoformable cast poly(methacrylate) which composition comprises
(a) at least from 95 % by weight of a syrup which is a solution of a 5 poly(methacrylate) in a curable monomeric methacrylate,
(b) from 0.05 to 0.1 % by weight of at least one initiator capable of initiating the curing of the curable monomeric methacrylate;
(c) from 0.0001 to 0 001 % by weight of a catalytic chain transfer agent or residue thereof which is or which is derived from a cobalt chelate, and optionally
10 (d) from 0.05 to 0 1 % by weight of a crosslinking agent;
(e) one or more of conventional additives selected from splitting aids, pigments, peak suppressors and stabilisers.
In a second aspect the present invention provides a thermoformable cast poly(methacrylate) sheet capable of being formed from a curable composition as hereinbefore
15 defined and having a Vicat Softening Point of at least 105°C and exhibiting a weight loss when subjected to thermogravimetπc analysis (TGA) between 260 and 300°C.
The poly(methacrylate) in the syrup is preferably formed from the same monomeric methacrylate which is also present in the syrup. Typically, the poly(methacrylate) represents from 5 to 35 %, more typically from 5 to 15 %, by weight of the syrup and preferably from 7 to
2025 %, more preferably from 7 to 9 % by weight, of the syrup Although the syrup may be prepared by the mixing of the poly(methacrylate) with the monomeric methacrylate, it is preferred that the syrup is prepared by partially polymerising the monomeric methacrylate so as to form the poly(methacrylate) in situ The conditions are controlled such that the poly(methacrylate) formed in situ is of an appropriate molecular weight for use in the
25 subsequent casting stage. Particularly preferred is when -he poly(methyl methacrylate) is formed in situ by the use of a catalytic chain transfer agent thereby providing improved control over both the molcular weight and polydispersivity
The poly(methyacrylate) and monomeric methacrylate are preferably derived from lower alkyl methacrylates, e.g. C, to C4 methacrylates, and in particular methyl methacrylate
30 The poly(methacrylate) may be a copolymer Additionally, one or more monomeric methacrylates may be used. Preferably, the poly(methacrylate) is a homopolymer, particularly poly(methyl methacrylate) and that the monomeric methacrylate is methyl methacrylate. Nevertheless, the use of the catalytic chain transfer agent allows for the incorporation of a minor proportion of one or more lower alkyl acrylates, C, to C4 acrylates, into the curable
35 composition without the deleterious effect of lowering the Vicat Softening Point being exhibited Where such an acrylate is used it is prefered that the acrylate is butyl acrylate
The at least one initiator may be one or more initiators commonly used in the preparation of conventional thermoformable cast poly(methacrylate) Suitable initiators include azodnsobutyronitrile, peroxydicarbonates such as di-isopropyl, di-n-butyl, di-isobutyl, 5 dicyclohexyl, or bιs-(4-t-butyl cyclohexyl) peroxydicarbonate, and t-butyl perpivalate Adventitiously, two or more initiators are chosen such that the lifetime and activity of the initiators are optimised during curing.
The catalytic chain transfer agent, or residue thereof, is or is derived from a cobalt chelate Suitable cobalt chelates are as described in US 4694054, US 5028677 and US 10 4680352 Particularly preferred is a cobalt chelate having the following general formula I
0 wherein R can be selected from of a variety of groups such as methyl and phenyl, particularly phenyl, and which is known generally as CoBF. Alternatively or additionally, the catalytic chain transfer agent is or is derived from cobaloxime.
The catalytic chain transfer agent is added at very low concentrations, i e. from 0.0001 to 0.001 , for example from 0.001 to 0.0005, % by weight on the curable composition 5 Preferably, the catalytic chain transfer agent is present from 0 00025 to 0.0003 % by weight, i e 2 5 to 3 ppm, in the curable composition At these levels of addition the average molecular weight ( of the cured curable composition (absent cross-linking agent) as determined by GPC (chloroform solvent; poly(methyl methacrylate) standard) is in the range 350000 to 500000 and in particular from 380000 to 480000. Increased amounts of the catalytic chain transfer agent reduce the molecular weight. Of further note is that it is believed that due to the manner in which the chain transfer agent effects the growing polymer chain, a surprisingly high proportion (compared with the proportion expected from using conventional free radical polymerisation) of the terminal groups of the poly(methacrylate) are not saturated. Consequently, when undergoing TGA the thermoformable cast poly(methacrylate) of the present invention shows some decomposition between 260 and 300°C typical of non-saturated terminal groups. Where the poly(methacryiate) is formed in situ by the use of a catalytic chain transfer agent as hereinbefore described the syrup will contain residues of such a chain transfer agent. Such residues will be present in the syrup at the levels hereinbefore stated. Subsequent casting and curing of the syrup may then use further amounts of the same or of a similar chain transfer agent or may employ more conventional catalysts. The crosslinking agent may be chosen from any conventionally used. Suitably, the crosslinking agent is chosen from at least one of ethylene glycol dimethacrytate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, triallyl cyanurate, allyl methacrylate, allyl acrylate, triallyl phosphate, diallyl maleate, methallyl acrylate, vinyl methacrylate and divinyl benzene. Particularly preferred is ethylene glycol dimethacrylate. Other conventional additives include splitting aids such as Texol (obtained from
Imperial Chemical Industries pic) and CR3009 (Wilco Corporation), pigment, peak suppressors such as Terpinolene (White Sea and Baltic Co Ltd) and stabiliser such as Irganox (Ciba Geigy).
The following examples illustrate the present invention. Example 1
A reactive mixture was prepared containing 2000 kg of monomeric methyl methacrylate, 100 g of UV stabiliser (Aduvex - The Great Lakes Fine Chemicals Ine), 1200 g of splitting aid (Texol) and 38 g of initiator (azodiisobutyronitrile - AZDN). The mixture was stirred and heated to about 82°C until a syrup containing about 8% by weight of poly(methyl methacrylate) was formed. Cast Poly(methyl methacrylate)
A curable composition was formed having the following composition:
Component % by weight
Splitting aid 0.2 Pigment 2.5
AZDN 0.018
Peak suppressor 0.01
Sheet stabiliser 0.05
Crosslinker 0.08 CoBF 0.00025
Syrup Balance
The curable composition was stirred and then poured into casting cells formed from sheets of glass so as to eventually provide sheets having thicknesses of 3.2 and 5 mm respectively. Curing followed a two stage heating process. The filled cells were first slowly heated to 90DC at which they were held for 1 hour. Thereafter the temperature was slowly raised to about 120CC at which they were held for a further 30 minutes. After curing, the cells were slowly cooled to room temperature.
The 5 mm thick sheets had a Vicat Softening Point (VSP) of 107.4°C and the 3 mm thick sheets had a VSP of 108.0°C. TGA of samples of the sheet showed decomposition occurring between 260 and
300°C which was absent from conventional thermoformable cast poly(methacryiate) prepared in the absence of cobalt chelate.
The ease with which sheets of the present invention could be thermoformed was compared against the ease at which commercially available sheets could be thermoformed. Sheets of each were preheated to different thermoforming temperatures and thereafter thermoformed into a standard shape. The accuracy to which the thermoformed sheet fitted the standard shape was then determined. Those commercial sheets formed from poly(methyl methacrylate) had to be preheated by about an additional 20°C above the preheat temperature used for the sheets of the present invention in order to achieve the same accuracy of fit. Conversely, the commercial sheets containing copolymer need not be heated by the same amount as the sheets of the present invention but had significantly inferior VSPs of about 100°C
Example 2
Example 1 was repeated except that the CoBF was replaced by cobaloxime. The 5mm sheet had a VSP of 109.2°C and showed a decomposition between 260 and 300CC when subjected to TGA.
Example 3
Example 2 was repeated except that the cobaloxime was used at a level of 3ppm. The 5mm sheet had a VSP of 109.6°C and again showed decomposition between 260 and 5 300°C.
Example 4
Example 1 was repeated except that the syrup contained 3.4 % by weight of butyl acrylate. The 3.2 mm sheet had a VSP of 105.4°C and the 5 mm sheet had a VSP of 105.2°C

Claims

Claims
1. A curable composition capable of being cured to form a thermoformable cast poly(methacrylate) which composition comprises
(a) at least from 95 % by weight of a syrup which is a solution of a poly(methacrylate) in a curable monomeric methacrylate;
(b) from 0.05 to 0.1 % by weight of at least one initiator capable of initiating the curing of the curable monomeric methacrylate;
(c) from 0.0001 to 0.001 % by weight of a catalytic chain transfer agent or residue thereof which is or which is derived from a cobalt chelate; and optionally (d) from 0.05 to 0.1 % by weight of a crosslinking agent;
(e) one or more of conventional additives selected from splitting aids, pigments, peak suppressors and stabilisers.
2. A curable composition as claimed as claim 1 wherein the poly(methacrylate) in the syrup represents from 5 to 15 % by weight of the syrup.
3. A curable composition as claimed in either claim 1 or claim 2 wherein the poly(methacrylate) and monomeric methacrylate are derived from C→ to C, methacrylates.
4. A curable composition as claimed in any one of claims 1 to 3 wherein the at least one initiator is one or more initiators selected from azodiisobutyronitrile, peroxoydicarbonates such as di-isopropyl, di-n-butyl, di-isobutyl, dicyciohexyl, or bis-(4-t-butyl cyclohexyl) peroxoydicarbonate, and t-butyl perpivalate.
5. A curable composition as claimed in any one of claims 1 to 4 wherein the catalytic chain transfer agent , or residue thereof, is or is derived from cobalt oxime.
6. A curable composition as claimed in any one of claims 1 to 4 wherein the catalytic chain transfer agent , or residue thereof, is or is derived from a cobalt chelate having the following general formula I
wherein R is methyl or phenyl.
7. A curable composition as claimed in any one of claims 1 to 6 wherein the crosslinking agent is selected from at least one of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tπethylene glycol dimethacrylate, triallyl cyanurate, allyl methacrylate, allyl acrylate, triallyl phosphate, diallyl maleate, methallyl acrylate, vinyl methacrylate and divinyl benzene.
8. A thermoformable cast poly(methacrylate) sheet formed from a curable composition as hereinbefore defined in any one of claims 1 to 7 having a Vicat Softenng Point of at least 105°C and exhibiting weight loss when subjected to thermogravimetric analysis (TGA) between 260 and 300°C. 9- thermoformable cast poly(methacrylate) sheet as claimed in claim 8 wherein the average molecular weight (M of the cured curable composition, absent cross-linking agent, as determined by GPC, using chloroform solvent and poly(methyl methacrylate) standard, is in the range 350000 to 500000 10. A thermoformed article produced from a thermoformable cast poly(methacrylate) sheet as defined in either claim 8 or claim 9.
EP97933765A 1996-07-25 1997-07-25 Thermoformable cast poly(methyl methacrylate) Withdrawn EP0914358A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9615607.0A GB9615607D0 (en) 1996-07-25 1996-07-25 Thermoformable cast poly(methyl methacrylate)
GB9615607 1996-07-25
PCT/GB1997/002020 WO1998004603A1 (en) 1996-07-25 1997-07-25 Thermoformable cast poly(methyl methacrylate)

Publications (1)

Publication Number Publication Date
EP0914358A1 true EP0914358A1 (en) 1999-05-12

Family

ID=10797475

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97933765A Withdrawn EP0914358A1 (en) 1996-07-25 1997-07-25 Thermoformable cast poly(methyl methacrylate)

Country Status (8)

Country Link
EP (1) EP0914358A1 (en)
JP (1) JP2000515200A (en)
AU (1) AU740435B2 (en)
CA (1) CA2261159A1 (en)
GB (1) GB9615607D0 (en)
NZ (1) NZ333853A (en)
WO (1) WO1998004603A1 (en)
ZA (1) ZA976677B (en)

Families Citing this family (12)

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Publication number Priority date Publication date Assignee Title
KR100593427B1 (en) 1998-03-12 2006-06-28 루사이트 인터내셔널 유케이 리미티드 Polymer composition
JP2002105126A (en) * 2000-07-18 2002-04-10 Soken Chem & Eng Co Ltd Highly viscoelastic acrylic polymer resin, its use and its production method
EP2436713A1 (en) 2010-09-29 2012-04-04 Sika Technology AG Two-Part Polyurethanes based on Hyperbranched Polymers
KR20130124359A (en) * 2011-01-27 2013-11-13 가부시키가이샤 오토네트웍스 테크놀로지스 Chain transfer agent, photosensitive composition, cured product of photosensitive composition, and method for curing photosensitive composition
CA2907916C (en) 2012-03-22 2020-08-11 The Regents Of The University Of Colorado Water compatible nanogel compositions
AU2017281706B2 (en) 2016-06-23 2021-05-13 The Regents Of The University Of Colorado, A Body Corporate Control of polymer network structures via nanogels
US11814512B2 (en) 2019-03-28 2023-11-14 Rohm And Haas Company Highly processable multi-stage flexible acrylic resins and process for making same
WO2020197797A1 (en) 2019-03-28 2020-10-01 Rohm And Haas Company Highly processable flexible acrylic resin
JP2022539323A (en) 2019-06-28 2022-09-08 ローム アンド ハース カンパニー Reactive acrylic polyolefin blend
JP2022540365A (en) 2019-06-28 2022-09-15 ローム アンド ハース カンパニー Allyl-functional thermoplastic additive for UV-curable soft acrylic resin clear films
CN114008091A (en) 2019-06-28 2022-02-01 罗门哈斯公司 Allyl functional thermoplastic additives for thermosetting polymers
KR20230002733A (en) 2020-04-21 2023-01-05 롬 앤드 하스 캄파니 Melt flow additives for polycarbonate and other engineering resins

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US4152506A (en) * 1978-04-26 1979-05-01 E. I. Du Pont De Nemours And Company Preparation of thermoformable methyl methacrylate sheets
US4694054A (en) * 1985-03-01 1987-09-15 E. I. Du Pont De Nemours And Company Cobalt(II) chelates as chain transfer agents in free radical polymerizations

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9804603A1 *

Also Published As

Publication number Publication date
GB9615607D0 (en) 1996-09-04
NZ333853A (en) 2000-07-28
CA2261159A1 (en) 1998-02-05
ZA976677B (en) 1998-12-27
AU3700997A (en) 1998-02-20
WO1998004603A1 (en) 1998-02-05
AU740435B2 (en) 2001-11-01
JP2000515200A (en) 2000-11-14

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