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Title:
LOW ORGANIC EMISSION RESINS
Document Type and Number:
WIPO Patent Application WO/1999/000433
Kind Code:
A1
Abstract:
The present invention relates to a composition comprising at least one alkoxylated bisphenol-A diacrylate or dimethacrylate, ethylene glycol dimethacrylate, and at least one vinyl monomer. The composition is suitable for use in the fiberglass reinforced plastic art. The composition possesses similar or superior physical properties compared to unsaturated polyester based speciality resins, including emitting lower levels of organic volatiles than typical resins used in the art.

Inventors:
Andrekanic, Ronald A. (2213 Cypress Drive, White Oak, PA, 15131, US)
Smeal, Thomas W. (12 Buena Vista Drive, Delmont, PA, 15626, US)
Pugach, Joseph (1035 Eagles Nest Lane, Monroeville, PA, 15146, US)
Application Number:
PCT/US1998/012985
Publication Date:
January 07, 1999
Filing Date:
June 23, 1998
Export Citation:
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Assignee:
ARISTECH CHEMICAL CORPORATION (USX Building, Law Dept. Room 1185, 600 Grant Stree, Pittsburgh PA, 14219-2704, US)
International Classes:
C08F220/30; C08F220/20; C08F222/10; (IPC1-7): C08F12/24
Foreign References:
US5501830A1996-03-26
GB2010868A1979-07-04
Other References:
See also references of EP 0920462A1
Attorney, Agent or Firm:
Gavlik, Robert R. (Aristech Chemical Corporation, Law Dept. USX Building, Room 1185, 600 Grant Stree, Pittsburgh PA, 15219-2704, US)
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Claims:
Claims
1. A composition consisting essentially of : (a) about 60 to about 90 wt% of at least one alkoxylated bisphenol A diacrylate or dimethacrylate; (b) about 5 to about 30 wt% ethylene glycol dimethacrylate ; and (c) about 5 to about 25 wt% of a vinyl monomer.
2. A compositon according to claim 1 wherein the alkoxylated bisphenolA diacrylate or dimethacrylate is about 7085 wt% of the composition.
3. A compositon according to claim 1 wherein the alkoxylated bisphenolA diacrylate or dimethacrylate is about 7080 wt% of the composition.
4. A composition according to claim 1 wherein the at least one alkoxylated bisphenolA diacrylate or dimethacrylate is selected from the group consisting of ethylene glycol dimethacrylates having 310 ethoxy groups.
5. A composition according to claim 1 wherein the at least one alkoxylated bisphenolA diacrylate or dimethacrylate is 6ethoxylated bisphenolA dimethacrylate.
6. A composition according to claim 1 wherein the ethylene glycol dimethacrylate is about 1025 wt% of the composition.
7. A composition according to claim 1 wherein the ethylene glycol dimethacrylate is about 1020 wt% of the composition.
8. A composition according to claim 1 wherein the vinyl monomer is about 10 20 wt% of the composition.
9. A composition according to claim 1 wherein the vinyl monomer is about 12 17 wt% f the composition.
10. A composition according to claim 1 wherein the vinyl monomer is selected from the group consisting of vinyl toluene, styrene, tbutyl styrene and divinyl benzene.
11. A composition according to claim 1 wherein the vinyl monomer is vinyl toluene.
Description:
LOW ORGANIC EMISSION RESINS Technical Field The present invention relates to polymer resin compositions useful in applications traditionally utilizing fiberglass reinforced plastic and low volatile emission specialty polyester resins.

Background of the Invention Fiberglass reinforced plastic resins are well known in the art. These resins find use in typical applications such as boat hulls, automotive parts, structural applications, pultrusion and mine bolts..

Low emission resins are also known in the art. For example, Smeal et al in U. S. Patent No. 5,501,830 disclose unsaturated polyester based resins that emit no more than 20.0 g/m2 as measured by Rule 1162 Standard Method for Static Volatile Emissions of the South Coast Air Quality Management District (California).

It is an object of the present invention to provide a composition having at least one alkoxylated bisphenol-A diacrylate or dimethacrylate, ethylene glycol dimethacrylate, and at least one vinyl monomer.

It is another object of the present invention to provide a composition useful in the fiberglass reinforced plastic art. Still another object of the present invention is to provide a composition having similar or superior physical properties to unsaturated polyester based resins, including emission of lower levels of volatile emissions during polymerization.

Summary of the Invention The present invention relates to a novel class of polymer resins comprising a pre-polymerized blend of: (1) at least one alkoxylated bisphenol-A diacrylates or dimethacrylates ("ABAD"); (2) ethylene glycol dimethacrylate ("EGDM"); and (3) at least one vinyl monomer.

The composition of the present invention finds use in applications typically reserved for fiberglass reinforced plastic and specialty polyester resin compositions. The resins of the present invention possess physical properties normally associated with polyester and styrenated resin compositions. However, the resins of the present invention emit lower levels of organic volatiles during polymerization than typical prior art resins used in fiberglass reinforced plastic applications.

Detailed Description of the Invention The ABAD of the present invention is present in an amount of about 60 to about 90 wt% of the total composition. Preferably, it is about 70 to about 85 wt%, and most preferably 70 to 80 wt%. The ABAD is preferably selected from the group consisting of ethoxylated bisphenol-A dimethacrylates ("EBAD") having from 3 to 10 ethoxyl groups. Most preferably, it is 6-EBAD. Mixtures of these EBADs are also within the scope of the present invention.

EGDM is about 5 to about 30 wt% of the composition. Preferably, it is about 10 to about 25 wt%, and most preferably 10 to 20 wt%.

The vinyl monomer is about 5 to about 25 wt% of the composition.

Preferably, it is about 10 to about 20 wt%, and most preferably 12 to 17 wt%. The vinyl monomer is preferably selected from the group consisting of styrene, vinyl toluene, t-butyl styrene and divinyl benzene. Most preferably, it is vinyl toluene.

The present invention is illustrated by, but not limited to the examples shown in Table I.

TABLE I LOE RESINS CONTAINING VARIOUS COMBINATIONS OF 3,6,ETHOXYLATEDBPADIMETHACRYLATE,10 <BR> DIMETHACRYLATE&VINYLMONOMERSETHYLENEGLYCOL K-15(1)R-14(1)Z-11(1)RESIN# COMPOSITION,% 5040-----3-EBPADIMETHACRYLATE 6-EBPA DIMETHACRYLATE-70 10-EBPA DIMETHACRYLATE 20 30 ETH. GYLCOL DIMETHACRYLATE 10 20 20 VINYL TOLUENE (MONOMER) 20 10 10 STYRENE ------------------ P-TERTIARY BUTYL ------------------ MODMODL, 25% HQ 0.040.050.05 COBALT 12% 0.300.300.30 POTASSIUM15% (COPROMOTER) 0.200. 200. 20 0.300.300.30DMAA(COPROMOTER) RESIN PROPERTIES (3) @77F,(CPS)355646BRKFLDVISCOSITY RM. TEMP. (77F) GEL TIME: (MIN.) 33.0 (2) 19.0 (2) 18.0 (2) 7.23.85.0INTERVAL,(MINUTES) PEAK EXOTHERM, (F) 313279 MINUTES31(2)46(2)37(2)BARCOLHARDNESS-45 1 HOUR40 (2) 38(2)(2) 2 HOUR40 (2) 48 (2) (2) 3 (2)48(2)39(2)40 4 HOUR 40 (2) 49 (2) 39 (2) 24 HOURS 42 (2) 49 () 38 (2) 1162 VOLATILE EMISSIONS, (G/M2) 21.8 (2) 9.7 (2) 10.3 (2) (MINUTES)12.05.03.5EMISSIONTIME, PHYSICAL PROPERTIES OF RESIN CLEAR CASTINGS: (3), (4) (PSI)8,960+/-1,3107,250+/-4908,000+/-300TENSILESTRENGTH, (MPSI)0,470+/-0.0110.470+/--0.0170.396+/-0.011TENSILEMODULUS , (%)2.5+/-0.51.9+/-0.23.3+/-0.4TENSILEELONGATION, FLEXURAL STRENGTH, (PSI) 1,02014,150+/-99012,800+/-2,030+/- FLEXURAL MODULUS, (MPSI) 0. 420 +/-0.008 0.400 +/-0.006 0.336 +/-0.066 HEAT DISTORTION TEMP: DUTL, 218175212 WATER 150F 0.51.110.9324HOURS: 7 DAYS: 1.141.45 (1) MODERATE AMOUNT OF FOAMING INITIALLY GENERATED WHEN MIXING THE INITIATOR IN WITH THE RESIN. FOAMING SHORTLY THEREAFTER DISSIPATES (2) SLT TACKY SURFACE OF CURED RESIN REMAINED FOR A COUPLE OF DAYS (3)-1.5% HIPOINT 90 MEKP ROOM TEMPERATURE INITIATOR (4) 2 HOUR ROOM TEMPERATURE (77F) CURE, 2 HOUR POSTCURE@100C TABLE I (CONTINUED-1) LOE RESINS COMBINATIONSOFVARIOUS 10ETHOXYLATEDBPADIMETHACRYLATE,3,6,AND DIMETHACRYLATE&VINYLMONOMERSETHYLENEGLYCOL A-12(1)U-12(1)A-13(1)RESIN# COMPOSITION,% ------50503-EBPADIMETHACRYLATE 6-EBPA DIMETHACRYLATE 20 20 i 10-EBPA DIMETHACRYLATE 70 ETH. 151010DIMETHACRYLATE VINYL TOLLIENE (MONOMER) 15 ------ STYRENE ------20------ P-TERTIARY BUTYL STYRENE 25%HQ(INHIBITOR)0.080.030.04MODL, COBALT 12% (PROMOTER) 0. 30 0.30 0.30 POTASSIUMPOTASSIUM15% (COPROMOTER) 0.200.20 DMAADMAA(COPROMOTER) 0.300.30 RESIN PROPERTIES (3) @77F,(CPS)393230BRKFLDVISCOSITY RM. TEMP. (77F) GEL TIME: (MIN.) 22.5 (2) 22.9 (2) 28.5 (2) 6.35.87.3INTERVAL,(MINUTES) (F)313337352PEAKEXOTHERM, ; BARCOL HARDNESS-45 MINUTES 32 (2) 40 (2) 39 (2) 1 HOUR 36 (2) 40 (2) 40 (2) 2 HOUR 37 (2) 42 (2) 42 (2) 3 (2)44(2)42(2)37 4 HOUR 37 (2) 48 (2) 42 (2) 24 HOURS 38 (2) 49 (2) 46 (2) : 1162 VOLATILE EMISSIONS, (G/M2) 4.8 (2) 16.3 (2) 30.9 (2) ! (MINUTES)9.027.519.0EMISSIONTIME, PHYSICAL PROPERTIES OF RESIN CLEAR CASTINGS: (3), (4) TENSILE STRENGTH, (PSI)7,700 +/-400 8,710 +/-840 7,230 570 (MPSI)0.402+/-0.0100.510+/-0.0120.514+/-0.018TENSILEMODULUS, TENSILE ELONGATION,(%) 0.52.0+/-0.31.6+/-0.2+/- (PSI)FLEXURALSTRENGTH, 640+/- 1,40014,770+/-1,520+/- FLEXURAL MODULUS, +/-0.005.443+/-0.0140.458+/-0.0030.352 HEATHEATDISTORTION TEMP:DTUL, F 233216 WATER ABSORPTION@150F 24 HOURS: 0.95 0.62 7 DAYS: 1.10 0.73 0.80 (1) MODERATE AMOUNT OF FOAMING INITIALLY GENERATED WHEN MIXING THE INITIATOR IN WITH THE RESIN. FOAMING SHORTLY THEREAFTER DISSIPATES (2) SLT TACKY SURFACE OF CURED RESIN REMAINED FOR A COUPLE OF DAYS (3)-1.5% HIPOINT 90 MEKP ROOM TEMPERATURE INITIATOR (4) 2 HOUR ROOM TEMPERATURE (77F) CURE, 2 HOUR POSTCURE@100C TABLE I (CONTINUED-2) LOE RESINS CONTAINING VARIOUS COMBINATIONS OF i 3,6, AND 10 ETHOXYLATED BPA DIMETHACRYLATE, ETHYLENE GLYCOL DIMETHACRYLATE & VINYL MONOMERS D-13(1)M-13(1)RESIN# COMPOSITION,% 5063-EBPADIMETHACRYLATE 20706-EBPADIMETHACRYLATE ------------10-EBPADIMETHACRYLATE ETH. GYLCOL DIMETHACRYLATE 20 20 VINYL TOLUENE ------------ STYRENE (MONOMER) 10 1 STYRENE------5P-TERTIARYBUTYL 25%HQ(INHIBITOR)0.020.03MODL, COBALT 12% (PROMOTER) 0.30 (COPROMOTER)0.200.20POTASSIUM15% DMAA (COPROMOTER) 0.30 RESIN PROPERTIES (3) @77F,(CPS)4890BRKFLDVISCOSITY RM. TEMP. (77F) GEL TIME: (2)18.0(2)25.0 5.85.3INTERVAL,(MINUTES) IPEAK EXOTHERM, (F) 329 286 BARCOL HARDNESS-45 MINUTES 45 (2) 42 (2) 1 HOUR 48 (2) 42 (2) 2 HOUR (2) 43 (2) 3 HOUR 51(2) 44 (2) 4 HOUR 53 (2) 45 (2) 24 HOURS 54 (2) 45 (2) EMISSION,(G/M2)14.5(2)5.4(2)1162VOLATILE (MINUTES)3.06.5EMISSIONTIME, PHYSICAL PROPERTIES OF RESIN CLEAR CASTINGS: (3), (4) TENSILE STRENGTH, (PSI) 8357,270+/-280+/- TENSILE MODULUS, (MPSI) 0,520 +/- 0.020 0.410 +/- 0.020 'TENSILE ELONGATION, (%) 1. 4 +/- 0. 2 2. 4 +/- 0. 3 FLEXURAL STRENGTH, (PSI) 12 636 +/-838 14,550 +/-1,160 FLEXURAL MODULUS, (MPSI) 0.460 +/-0.028 0.371 +/-0.006 HEAT DISTORTION TEMP: DTUL, F 250 208 WATERABSORPTION@150F 24 HOURS: 0.64 1.27 7 DAYS: 1.04 1. 62 (1) MODERATE AMOUNT OF FOAMING INITIALLY GENERATED WHEN MIXING THE INITIATOR IN WITH THE RESIN. FOAMING SHORTLY THEREAFTER DISSIPATES (2) SLT TACKY SURFACE OF CURED RESIN REMAINED FOR A COUPLE OF DAYS (3)-1.5% HIPOINT 90 MEKP ROOM TEMPERATURE INITIATOR (4) 2 HOUR ROOM TEMPERATURE (77F) CURE, 2 HOUR POSTCURE@100C