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Thermoset composition, method, and article

a technology of thermoset and composition, applied in the field of thermoset composition, method and article, can solve the problem that the low-profile additives known for polyester thermoset are ineffective in the poly(arylene ether)-containing composition, and achieve the effect of reducing its viscosity

Inactive Publication Date: 2003-11-20
SABIC INNOVATIVE PLASTICS IP BV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0011] After extensive investigations, the present inventors have characterized and identified polymeric additives that reduce shrinkage on molding and improve as-molded surface characteristics of poly(arylene ether)-containing thermoset compositions.
[0032] In a preferred embodiment, the capped poly(arylene ether) may be prepared by reaction of an uncapped poly(arylene ether) with an anhydride in an alkenyl aromatic monomer as solvent. This approach has the advantage of generating the capped poly(arylene ether) in a form that can be immediately blended with other components to form a curable composition; using this method, no isolation of the capped poly(arylene ether) or removal of unwanted solvents or reagents is required.
[0041] There is no particular limitation on the molecular weight or intrinsic viscosity of the functionalized poly(arylene ether). In one embodiment, the composition may comprise a functionalized poly(arylene ether) having a number average molecular weight up to about 10,000 atomic mass units (AMU), preferably up to about 5,000 AMU, more preferably up to about 3,000 AMU. Such a functionalized poly(arylene ether) may be useful in preparing and processing the composition by reducing its viscosity.
[0042] In another embodiment, the composition may comprise a functionalized poly(arylene ether) having an intrinsic viscosity of about 0.08 to about 0.30 deciliters per gram (dL / g), preferably about 0.12 to about 0.30 dL / g, more preferably about 0.20 to about 0.30 dL / g as measured in chloroform at 25.degree. C. Generally, the intrinsic viscosity of a functionalized poly(arylene ether) will vary insignificantly from the intrinsic viscosity of the corresponding unfunctionalized poly(arylene ether). Specifically, the intrinsic viscosity of a functionalized poly(arylene ether) will generally be within 10% of that of the unfunctionalized poly(arylene ether). These intrinsic viscosities may correspond approximately to number average molecular weights of about 5,000 to about 25,000 ANU. Within this range, a number average molecular weight of at least about 8,000 AMU may be preferred, and a number average molecular weight of at least about 10,000 AMU may be more preferred. Also within this range, a number average molecular weight up to about 20,000 AMU may be preferred. Such a functionalized poly(arylene ether) may provide the composition with a desirable balance of toughness and processability. It is expressly contemplated to employ blends of at least two functionalized poly(arylene ether)s having different molecular weights and intrinsic viscosities.

Problems solved by technology

However, low-profile additives known for polyester thermosets are ineffective in the poly(arylene ether)-containing compositions.

Method used

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  • Thermoset composition, method, and article
  • Thermoset composition, method, and article
  • Thermoset composition, method, and article

Examples

Experimental program
Comparison scheme
Effect test

examples 25-30

[0150] Six samples were prepared varying in crosslinker amount, and polymeric additive and amount. The base resin for all samples was a 50 weight percent solution in styrene of a methacrylate-capped poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.12 dL / g.

[0151] The crosslinker was trimethylolpropane triacrylate (TMPTA) or trimethylolpropane trimethacrylate (TMPTMA). The initiator was t-butyl peroxy-2-ethylhexanoate, obtained as LUPEROX.RTM. 26 from Atofina Chemicals.

[0152] Three different polymeric additives were used. The additive designated "PEB Kraton L1203" in Table 3 was a monohydroxy-terminated poly(ethylene-butylene) having a hydroxyl equivalent molecular weight of 4,200 AMU, an approximate hydroxyl functionality of 0.9, and a specific gravity of 0.88 g / cc, obtained as KRATON.RTM. L1203 from Kraton Polymers. "PB Lithene N4-9000" was a liquid polybutadiene having a number average molecular weight of 9,000, 10-20% 1,2 vinyl microstructure, 50-60% trans...

example 37

, COMPARATFVE EXAMPLE 5

[0158] Two samples were prepared with and without 10 weight percent of a 50:50 weight / weight mixture of polybutadiene and poly(ethylene-butylene). Components were the same as those described above for Examples 38-43.

[0159] Molding was performed at 150.degree. C. and 1,200 psi. Shrinkage, orange peel, and waviness values represent averages for two samples.

[0160] Compositions and properties are presented in Table 5. The results show that the combination of polybutadiene and poly(ethylene-butylene) is particularly effective at reducing shrinkage (to the point of causing slight expansion in Ex. 44), orange peel, and waviness.

5 TABLE 5 C. Ex. 5 Ex. 37 50 / 50 0.12 IV PPO-MAA / styrene (pbw) 80 80 Trimethyloipropane trimethacrylate (pbw) 20 20 Polybutadiene (pbw) -- 5 Poly(ethylene-butylene) (pbw) -- 5 Shrinkage (%) 0.095 -0.016 Orange Peel 45 26 to 35 Waviness 1670 135 to 330

examples 38-55

[0161] Eighteen samples were prepared varying in the type and amount of crosslinker, the type and amount of polymeric additive, the type and amount of initiator, and the molding temperature.

[0162] The base resin for all examples was a methacrylate-capped poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.12 dL / g. It was used in the form of a 50 weight percent solution in styrene. The initiator t-butyl peroxy-2-ethylhexanoate was obtained as LUPEROX.RTM. 26 from Atofina Chemicals. The initiator t-butyl perbenzoate was obtained as LUPEROX.RTM. P from Atofina Chemicals. The crosslinker was either trimethylolpropane triacrylate (TMPTA) or trimethylolpropane trimethacrylate (TMPTMA).

[0163] Five different polymeric additives were employed. A dihydroxy-terminated poly(ethylene-butylene) having a weight average molecular weight of 1,700 AMU was obtained as KRATON.RTM. L2203 from Kraton Polymers. A monohydroxy-terminated poly(ethylene-butylene) having a weight average ...

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Abstract

A curable composition includes a functionalized poly(arylene ether), an alkenyl aromatic monomer, an acryloyl monomer, and a polymeric additive effective selected from polystyrene, poly(styrene-maleic anhydride), poly(styrene-methyl methacrylate), polybutene, poly(ethylene-butylene), poly(vinyl ether), poly(vinyl acetate), and combinations thereof. The composition exhibits low shrinkage on curing and improved surface smoothness. It is useful, for example, in the manufacture of automotive body panels.

Description

[0001] Thermoset molding compositions known in the art are generally thermosetting resins containing inorganic fillers and / or fibers. Upon heating, thermoset monomers initially exhibit viscosities low enough to allow for melt processing and molding of an article from the filled monomer composition. Upon further heating, the thermosetting monomers react and cure to form hard resins with high stiffness.[0002] One industrial use of thermoset compositions is the molding of automotive body panels. These panels preferably exhibit high dimensional stability and a smooth as-molded surface. It is also preferred that the dimensions of the molded parts conform closely to those of the molds used to prepare them.[0003] Thermoset compositions based on unsaturated polyester resins and styrene are known to exhibit reduced shrinkage and improved surface properties when they incorporate a so-called low-profile additive, such as a polymethacrylate copolymer. See, for example, V. A. Pattison et al. J. ...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C08L71/00B32B1/00C08F279/02C08F283/08C08G65/48C08K3/00C08K5/00C08L23/18C08L71/12C08L101/00
CPCC08F279/02C08F283/08C08G65/485C08G2650/04Y10T428/13C08L71/126C08L23/18Y10T428/1352C08L2666/04
Inventor YEAGER, GARY WILLIAMMERFELD, GLEN DAVIDDUFFEY, BRYAN
Owner SABIC INNOVATIVE PLASTICS IP BV
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