GB2217722A - Vinyl terminated urethane containing resins - Google Patents

Vinyl terminated urethane containing resins Download PDF

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Publication number
GB2217722A
GB2217722A GB8909859A GB8909859A GB2217722A GB 2217722 A GB2217722 A GB 2217722A GB 8909859 A GB8909859 A GB 8909859A GB 8909859 A GB8909859 A GB 8909859A GB 2217722 A GB2217722 A GB 2217722A
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Prior art keywords
resin
aromatic solvent
polyurethane
group
polyisocyanate
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GB8909859D0 (en
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Julie Linda Reeves
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Scott Bader Co Ltd
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Scott Bader Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/487—Polyethers containing cyclic groups
    • C08G18/4879—Polyethers containing cyclic groups containing aromatic groups

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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)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

A method of preparing a polyurethane having terminal ethylenic unsaturation comprises the steps of (a) dissolving a polyol in an aromatic solvent having at least one ethylenically unsaturated side chain, thereafter (b) reacting the polyol with a polyisocyanate to form a polyurethane/aromatic solvent mixture, and thereafter (c) reacting the said mixture with a compound capable of providing the polyurethane with the terminal ethylenic unsaturation. The final product is a resin comprising the polyurethane having terminal ethylenic unsaturation dissolved in the aromatic solvent.

Description

VINYL TERMINATED URETHANE CONTAINING RESINS This invention relates to the manufacture of vinyl terminated, urethane containing resins in the presence of a copolymerisable solvent.
In EP-A-0064809 we are taught that vinyl terminated urethanes can be made in the presence of methyl methacrylate, but are positively discouraged from the use of styrene as the copolymerisable solvent on the grounds that the resulting resin product has very poor storage stability and slow gel times.
However, methyl methacrylate is classified as highly flammable and is thus potentially hazardous. Furthermore, many laminators object to its odour.
US-A-3297745 describes the preparation of vinyl terminated polyurethanes in which each of a glycol, diisocyanate and the compound capable of providing the terminal unsaturation are reacted together in a solvent which may be styrene.
However, we find that the mechanical properties of the final product tend to be inadequate.
Styrene is commonly used as the solvating monomer in laminating resins and fabricators are familiar with taking the level of precautions necessary for its safe handling.
Accordingly, it would be particularly advantageous if a process could be found which enabled the production of a resin containing unsaturated monomer, especially styrene, which did not suffer from the above disadvantages.
It was both significant and unexpected to find a process by which resin products of excellent storage stability and hence commercial usefulness could be manufactured using styrene and other allied copolymerisable solvents, which products could be moulded, especially by the so-called hand lay-up technique to give mouldings having excellent chemical resistance and mechanical properties.
In a process of the present invention, a linear, preferably aromatic polyol, especially diol, present in solution in an aromatic solvent having at least one unsaturated side chain, is firstly reacted with a polyisocyanate.
The diol should be dissolved in at least a portion of the solvent, for example by gently heating to a temperature between 55 and 65"C inclusive, prior to admixture with the polyisocyanate After conducting the reaction between the diol and the polyisocyanate to form a urethane/solvent mixture, this product is reacted with a compound capable of providing terminal unsaturation on the urethane so as to provide a resin comprising a terminally unsaturated urethane and an unsaturated aromatic solvent for the urethane, the terminally unsaturated urethane and the unsaturated aromatic solvent being copolymerisable with one another under free radical polymerization conditions.
The above-mentioned diol may be represented by HO-Y-R-Y'-OH where R = (a) an aromatic ring or fused aromatic rings, any of which aromatic ring or rings is optionally substituted, or (b) the group -C6H4-X-C6H4 - where -X- is absent, -CH2-, -C(CH3)2-, or -SO2- and the or each aromatic ring may be substituted, or (c) an alicyclic structure, for example, the dicyclopentadiene nucleus or hydrogenated versions of (a) or (b).
-Y- and -Y'- are each, indepenently of one another, absent or are a group (-ZO-) where
and n = 1 - 30.
Examples of suitable diols are 2,2-bis(4-hydroxyphenyl) propane (Bisphenol A); bis (4-hydroxyphenyl) sulphone (Bisphenol S) or polyalkylated derivatives of Bisphenol A such as the commercially available DianolR (Ketjen) series of compounds (which are polyethoxylated or polypropoxylated derivatives of Bisphenol A).
The solvent is liquid at ambient temperature, aromatic and has unsaturation contained in one or more linear side chains, for example, styrene, vinyl toluene, p-methyl styrene, and diallyl phthalate.
The polyisocyanate is reacted with the solvated diol to form a urethane linkage at each hydroxyl location. The rate of isocyanate addition is used to control the temperature to within the range 60 - 75"C. The isocyanate may be difunctional for example isophorone diisocyanate (IPDI), diphenyl methane-4',4'-diisocyanate (MDI) or have a functionality of between 2.0 and 3.0 as found in the industrially available polymeric MDI's for example the SuprasecR (ICI) and VoranateR (Dow) series.
This product is then reacted with the compound capable of providing terminal unsaturation. This reaction may be carried out by adding enough of the compound, which may be a compound containing a reactive OH group and an ethylenically unsaturated group (hereinafter called "an unsaturated, hydroxy compound") to react with all the remaining isocyanate groups, the maximum reaction temperature allowed being between, say, 65 - 85"C. In practice a slight stoichiometric excess of the unsaturated, hydroxy compound is added to ensure that only a minimal level of isocyanate groups remain after an acceptable reaction period. Under the free-radical conditions which obtain on subsequent curing, unreacted compound will copolymerise with the reactive solvent, but the residue is calculated to be small enough not to affect the properties of the cured resin.The compound is preferably a hydroxyalkyl acrylate or methacrylate; especially preferred are where the hydroxy group is provided by a 2-hydroxyalkyl group containing from 2-4 carbon atoms, for example, 2 hydroxypropyl acrylate or methacrylate, or 2-hydroxyethyl acrylate or methacrylate.
To prevent premature polymerisation of the solvent during the reaction process, conventional vinyl inhibitors may be used, for example hydroquinone, toluhydroquinone, 1,4naphthaquinone and tertiary butyl catechol.
To assist the reaction between the unsaturated hydroxy compound and the polyisocyanate, a catalyst, which may be any of those known to those skilled in the art of polyurethane production, may be used, for example an organometal salt, especially diyn-butyl tin dilaurate.
On completion of the reaction, further solvent, copolymerisable with the reaction solvent and/or terminally unsaturated urethane (not necessarily the same as that used during the reaction), may be added to the product to adjust the resin to solvent (monomer) ratio or modify the solution rheology.
Curing of the resins can be accomplished by the use of organic free radical catalysts and heat, or peroxides and accelerators or UV light.
These resins may be combined with inert fillers such as silica, calcium carbonates, mica, talc, and clays and/or coloured by means of pigments.
Rheological properties can be further modified by the incorporation of thixotropic agents such as fumed silica (AerosilR or CabosilR) to produce, for example, gel coat compositions and adhesives pastes.
Product resins may also be combined with other free radical curing resins, for example unsaturated polyester and vinyl ester resins.
The resins are particularly suitable for moulding by the hand lay-up technique for which the composition preferably contains from 15-60%, more preferably 20-50%, by weight of the total weight of the composition of the ethylenically unsaturated aromatic solvent.
Provided that sufficient aromatic solvent is present to dissolve the polyol for reaction thereof with the polyisocyanate, all or a part of the aromatic solvent may be included in the resin at any time before, during or after formation of the terminally unsaturated polyurethane.
The polyol should be dissolved in a portion, or in all of the aromatic solvent prior to admixture thereof with the polyisocyanate.
The polyisocyanate may also be dissolved in the aromatic solvent prior to reaction thereof with the polyol, but in this case care must be taken to ensure that the aromatic solvent is dry before introduction into it of the polyisocyanate.
Where a relatively large proportion of aromatic solvent is desired, the reactions of the polyol with the isocyanate and polyurethane with the compound providing the terminal unsaturation may be carried out in the presence of a portion of the total aromatic solvent required, the remainder being added thereafter.
Typically the above reactions are carried out in a proportion of aromatic solvent which will amount to 20-35% by weight of the final composition, another 15-30% aromatic solvent being added after completion of the reaction.
The following Examples serve to illustrate the invention.
In each of the Examples, the physical properties of the cast resins were determined according to the following standard methods: 1) Heat deflection temperature - BS 2782 Part 1 Method 1218 equivalent to ISO 75.
2) Tensile properties - BS 2782 Part 3 Method 320C equivalent to ISO R527.
3) Water absorption over 7 days - BS 2782 Method 430A and B equivalent to ISO 62.
4) Unnotched Charpy Impact - BS 2782 Method 351A equivalent to ISO R179.
5) Barcol Hardness - measured on a Barcol Hardness testing machine of Barker Coleman Co., Model No. GYZJ 934.1, to a scale on which glass measures 100.
The resin was catalysed using (i) 2% by weight of the composition of Butanoxe LPT, a commercially available catalyst which is a 50t solution of methyl ethyl ketone peroxide (MEKP) in a non-volatile plasticiser, and (ii) 2% by weight of the composition of a cobalt octoate accelerator (a solution in styrene containing 1% of cobalt metal), then cast in sheets. After gelation 24 hours was allowed at room temperature before the sheets were post cured for 3 hours at 80 C before testing. Cast resin used for heat deflection testing, was post cured for 5 hours at 80 C followed by a further 3 hours at 120 C.
Example 1 250 Kg of a resin material was made in a stainless steel reactor equipped with a stirrer, reflux condenser, nitrogen inlet, thermometer, connection to a feed vessel, and a jacket for steam heating or water cooling. All quantities given are as per 1,000 parts by weight.
98.636 parts of DianolR 33, a propoxylated Bisphenol A (Ketjen), was dissolved in 216.138 parts of styrene in the presence of 0.1 parts of 1,4-naphthaquinone and 0.19 parts of Inhibitor T, a commercially available inhibitor which is a 30% solution of toluhydroquinone in ethyl glycol Cellosolve. The temperature was raised to 60"C.
Over a period of from 45 - 60 minutes, 242.795 parts of VoranateR M580 (a polymeric MDI of functionality 2.8) was added during which the temperature was controlled within the range 60 - 65"C. After the addition the temperature was raised to 700C and the reaction continued for .a further 1.5 - 2.0 hours until determination of the residual isocyanate content indicated that the hydroxy reaction was complete.
0.1 parts of Mellite 12R (M and T Chemicals Inc), dibutyl tin dilaurate, was added followed by the addition of 168.241 parts of 2-hydroxypropyl methacrylate, containing 0.19 parts of Inhibitor T. Addition took approximately 1 hour.
The temperature was then raised progressively to a maximum of 750C over a further 3 - 4 hours until the measured isocyanate content was less than 0.5%.
The batch was cooled and a further 0.19 parts of Inhibitor T added together with 273.420 parts of styrene.
When catalysed and cured as a cast resin as described above, the following properties were achieved; heat distortion ("deflection") temperature 1290C, tensile strength 84.0 MPa, tensile modulus 3.2 GPa, elongation at break 6.8t and water absorption over 7 days 0.2%.
Storage stability of the uncatalysed resin was found to be in excess of six months at ambient temperature.
Example 2 A 5 Kg batch of a resin material was made in an electrically heated glass reactor fitted with a stainless steel stirrer, thermometer, nitrogen inlet, reflux condenser and connected to a feed vessel.
All quantities were proportionally the same as for Example 1 except for an exact molar substitution of Dianol 3310 for Dianol 33 (Dianol 3310 contains a higher level of propoxylation).
Reaction conditions and times and curing conditions were as stated in Example 1. Cured properties measured on cast samples were as follows: heat deflection temperature 760 C, tensile strength 57.8 MPa, tensile modulus 2.73 GPa, elongation at break 8.22% and Unnotched Charpy Impact strength 34.3 KJ/m.
Storage stability of the uncatalysed resin was in excess of 6 months at ambient temperature.
Example 3 A resin was manufactured according to the method of Example 2 but containing IsonateR 400, a polymeric MDI of functionality 2.1 (manufactured by Dow) in place of the Voranate M580. The reactant quantitites in parts per 1000 by weight were as follows: Dianol 33 116.318, styrene 254.905 + 159.937, Isonate 400 244.939 2-hydroxypropyl methacrylate 223.689, Inhibitor T 0.336 and MelliteR 12 0.100. No l,4-baphthaquinone was used in this example.
Cured properties measured on cast samples were: heat deflection temperature 1080 C, tensile strength 81.9 MPa, tensile modulus 2.73 GPa, elongation at break 3.9%.
Storage stability of the uncatalysed resin was in excess of 6 months at ambient temperature.
Example 4 Manufactured according to the Method of Example 3 but containing the diisocyanate IPDI (in place of Isonate 400) and a lower level of styrene. Quantities were Dianol 33 153.596, styrene 336.630, IPDI 214.149, 2-hydroxypropyl methacrylate 295.377, Inhibitor T 0.444, MelliteR 12 0.10.
Cured properties measured on cast samples were tensile strength 72.4 MPa, tensile modulus 3.42 GPa, and elongation at break 2.3%.
Storage stability of the uncatalysed resin was in excess of 6 months at ambient temperature.
Example 5 Manufactured according to the method of Example 2, but using diallyl phthalate (in place of styrene) as the copolymerisable solvent to produce an adhesive paste which was hardened and cured by a peroxy catalyst and heat.
Quantities were Dianol 3310 374.779, diallyl phthalate 99.819, Voranate M 580 310.479, MelliteR 12 0.100, 2hydroxy propyl methacrylate 214.333 and Inhibitor T 0.147.
Storage stability of the uncatalysed paste was in excess of 6 months at ambient temperature.
Example 6 Several batches of resin were prepared and cured using the same starting materials, proportional amounts and reaction and curing conditions as those of Example 1.
Results derived from standard tests and castings of these resins are given in the Table 1 below, these figures representing respective property ranges for the various batches.
Comparative Example A resin was prepared using the same formulation as that of Example 1. However, in this Comparative Example, each of the propoxylated Bisphenol A, polymeric MDI, 2-hydroxypropyl methacrylate and styrene were simultaneously admixed together. As the stirred reactor was heated, the solid components dissolved in those liquid components in which they were soluble at the same time as the reaction was beginning. The resin was catalysed, cured and tested, in the same manner as the batches of Example 6, to determine the mechanical properties.
The results are shown in the Table 1 below.
Table 1 Example 6 Comparative Example Heat Deflection Temperature "C 125 - 130 138 Percentage Elongation at Break % 6 - 7 2.0 Tensile Strength MPa 75 - 85 57.4 Tensile Modulus GPa 3.0 - 3.5 3.34 Example 7 Respective samples of one of the resin batches of Example 6 were tested for chemical resistance, in particular, resistance to neutral, acid, and alkaline aqueous environments, and to the organic solvent toluene.
The results are shown in Table 2, from which it can be seen that castings from the resin are highly resistant to all aqueous environments, whether neutral, acid or alkaline.
The toluene resistance results demonstrated that a casting from a resin prepared by the method of the invention had considerable resistance to toluene. Indeed the casting was much more resistant to toluene than a casting prepared in the same manner but from Derakane 411-45 (Dow). Thus, when the casting prepared from this commercially available resin (considered to have particularly good chemical resistance properties) was subjected to the toluene resistance test given in Table 2, the casting disintegrated after only 1 month, whereas a period of over 3 months elapsed before disintegration of the casting of the resin prepared by the method of the invention.
Table 2 CHEMICAL RESISTANCE RESIN Batch No PD 7447/49295 Flexural Flexural B.H* Time exp. Environment strength Modulus ret Absorption MPa GPa % CONTROL 131.2#3.0 3.37#0.09 37#1 - 25% Hydrochloric 111.8#16.0 3.6310.17 32i2 Acid @ 40 C 85% 108% 86% 0.27 25% Sodium 111.5#16.6 3.67#0.14 32#0 0.13 1 Month Hydroxide @ 40 C 85% 109% 86% Distilled Water 130.9#10.0 3.78#0.15 30#1 0.41 @ 65 C 100% 112% 81% Toluene @ 40 C** 70#3.1 2.24#0.27 0 10.9 54% 59% 25% Hydrochloric 109.2t26.0 3.51#0.17 30;1 Acid @ 40 C 83% 104% 81% 0.47 25% Sodium 124.0#20.3 3.38#0.16 30#2 0.33 6 Months Hydroxide @ 40 C 94% 100% 81% Distilled Water 111.0#28.9 3.59#0.16 30#1 0.60 @ 65 C 85% 106 81% 25% Hydrochloric 122.6#20.0 3.74#0.21 35#1 0.65 Acid @ 40 C 93% 111% 95% 25% Sodium 140.2t2.5 3.60#0.20 36+0 12 Months Hydroxide @ 40 C 107% 107% 97% 0.51 Distilled Water 111.6#8.0 3.80#0.09 37#2 @ 65'C 85% 113% 100% 0.75 ** The sample disintegrated after 3 months, 1 week * Barcol Hardness retention As can be seen, especially from Table 1, as compared with the castings from resins prepared by simultaneous reaction of glycol, polyisocyanate and hydroxyacrylate, the castings from resins prepared by the method of the present invention have superior tensile strength and elongation values without increased modulus and with only a modest reduction in heat deflection temperature; in short, they have an enhanced property profile.
Furthermore, the resins have excellent chemical resistance.
The following Examples 8 and 9 illustrate respectively a blend of a resin in accordance with the invention with an unsaturated polyester resin and a gelcoat formulation containing a resin in accordance with the invention.
Example 8 Blend of the resin of Example 1 and an Unsaturated Polyester Resin The polyester was based on isophthalic acid, and propylene and dietheylene glycols. When cured as a cast'sheet its heat deflection temperature was 75"C and elongation at break between 3.0 and 3.5%.
A 50:50 parts by weight blend with the resin of Example 1 gave a heat deflection of 95"C and elongation at break of 4.58.
As expected the properties were midway between the extreme values as represented by the component resins.
Example 9 A Gelcoat Formulation A higher viscosity version of Example 1 was prepared i.e.
containing less styrene (57% solids c.f. 50% solids), but otherwise similar. A gelcoat for the resin was made according to the following 1000 part by weight formulation.
Resin 957,5 Styrene (additional to the above) 16.5 Cabosil M5 (a fumed silica) 25.0 A 10% solution of MS200 (a polydimethyl siloxane) in styrene 1.0 The gelcoat produced was suitable for tooling (mould making purposes) and had the following viscosity profile when measured on a Ferranti Shirley Viscometer.
D cone (4500/s) 12 poise A cone (6.0/s ) 60-100 poise A cone (0.6/s ) . 380-450 poise

Claims (17)

  1. CLAIMS: 1. A method of preparing a polyurethane having terminal ethylenic unsaturation, which method comprises the steps of (a) dissolving a polyol in an aromatic solvent-having at least one ethylenically unsaturated side chain, thereafter (b) reacting the polyol with a polyisocyanate to form a polyurethane/aromatic solvent mixture, and thereafter (c) reacting the said mixture with a compound capable of providing the polyurethane with the terminal ethylenic unsaturation.
  2. 2. A method according to claim 1, which includes the additional step of adding additional aromatic solvent having at least one ethylenically unsaturated side chain subsequent to step (c).
  3. 3. A method according to claim 1 or claim 2, wherein the final product is a resin comprising the polyurethane having terminal ethylenic unsaturation dissolved in the aromatic solvent, which aromatic solvent is present, in an amount, by weight of the resin, of from 15-60% inclusive.
  4. 4. A method according to claim 3, wherein the aromatic solvent is present in an amount, by weight of the resin, of from 20-50% inclusive.
  5. 5. A method according to any preceding claim, wherein the aromatic solvent is styrene, vinyl toluene, p-methyl styrene or diallyl phthalate.
  6. 6. A method according to any preceding claim, wherein the polyol is a diol of the formula HO-Y-R-Y' -OH wherein R is (a) an optionally substituted aromatic group, or (b) the group -C6H4-X-C6H4-, where X is absent or is -CH2, -C(CH3)2- or -SO,-, or (c) an alicylic group, -Y- and -Y'- are each, independently of one another, absent or are a group (-ZO-) where -Z- is the
    group -CH2CH2- or -CH2CH-, and CH n is 1-30. CH3
  7. 7. A method according to claim 6, wherein the diol is 2,2 -bis(4-hydroxyphenyl) propane, a polyalkoxylated derivative thereof or bis(4-hydroxyphenyl) sulphone.
  8. 8. A method according to any preceding claim, wherein the polyisocyanate is a diisocyanate.
  9. 9. A method according to claim 8, wherein the diisocyanate is isophorone diisocyanate or diphenyl methane-4,4'diisocyanate.
  10. 10. A method according to claim 7, wherein the polyisocyanate has a functionality between 2 and 3.
  11. 11. A method according to claim 10, wherein the polyisocyanate is a polymer of diphenyl methane-4,4' diisocyanate.
  12. 12. A method according to any preceding claim, wherein the compound capable of providing the polyurethane with the terminal unsaturation is a compound containing a reactive hydroxyl group.
  13. 13. A method according to claim 12, wherein the said compound containing a reactive hydroxyl group and an ethylenically unsaturated group is a hydroxyalkyl acrylate or methacrylate.
  14. 14. A method according to claim 13, wherein the hydroxyalkyl acrylate or methacrylate is 2-hydroxypropyl acrylate or methacrylate or 2-hydroxyethyl acrylate or methacrylate.
  15. 15. A method according to any preceding claim wherein the reaction of step (b) is carried out at a temperature of from 60-75"C inclusive.
  16. 16. A method according to any preceding claim wherein the reaction of step (c) is carried out at a temperature of from 65-85"C inclusive.
  17. 17. A method of preparing an article of thermoset material which method comprises preparing a resin prepared by a method according to any preceding claim and curing the resin to form the said article.
GB8909859A 1988-04-29 1989-04-28 Vinyl terminated urethane containing resins Withdrawn GB2217722A (en)

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GB2217722A true GB2217722A (en) 1989-11-01

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US5306764A (en) * 1992-09-03 1994-04-26 China Technical Consultants Inc. Water dispersible polyurethane and process for preparation thereof
EP0599461A1 (en) * 1992-10-06 1994-06-01 Ciba-Geigy Ag Curable formulations
EP0713015A1 (en) 1994-10-28 1996-05-22 Basf Aktiengesellschaft Self-supporting mastic for dowels used in the chemical fastening technology
WO2005103121A1 (en) 2004-04-26 2005-11-03 Dsm Ip Assets B.V. Method for photocuring of resin compositions
WO2012076687A2 (en) 2010-12-09 2012-06-14 Dsm Ip Assets B.V. Method for preparing urethane methacrylate resin
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