Emulsion polymerization

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...

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524494, 524803, C08L 3100

Patent

active

053649044

DESCRIPTION:

BRIEF SUMMARY
FIELD OF THE INVENTION

This invention relates to copolymer emulsions, and particularly concerns copolymer emulsions suitable for use as sizing agents for glass fibre prior to incorporation of bulk glass fibre in thermoplastic polymers.


BACKGROUND OF THE INVENTION

Glass fibre is a form of glass produced by a technique in which molten glass is passed through a multi apertured mould to form filaments. These filaments have: small diameters usually in the range of 1 micron to 4 micron, typically about 2 micron, although diameters outside this range are known for special applications. These filaments are then subjected to a sizing operation, using a sizing agent, possibly in combination with other additives, to provide bonding of the filaments together to form strands or fibres.
One application of glass fibres is to provide reinforcement and flexibility to thermoplastic polymer articles, typically made of polymers such as polypropylene, polyamides and polycarbonates, and usually shaped by injection moulding.
The sizing agent additionally functions to protect the filaments from breaking during handling, and must also be To obtain the most efficient sizing of glass filaments, the emulsion should be free of particles above 2 microns, and preferably has a weight mean particle diameter of above about 0.2. micron, more preferably above about 0.4 micron. Mean weight particle diameters of the copolymer particles are typically in the range of 0.4 to 1.0 micron.
Examples of the acrylate monomers are methyl methacrylate (homopolymer Tg of 100 .degree. C.), ethylhexyl acrylate (Tg of -60 .degree. C.), butyl acrylate (Tg of -50.degree. C.) and ethyl acrylate (Tg of -22.degree. C.). A proportion of a carboxylic monomer, for example acrylic acid, may also be present to improve adhesion to the surface of glass. Other monomers may be incorporated at minor levels, that is up to 10% by weight of the total monomers, usually up to 5%. Examples of these monomers are vinyl silanes, cross linking agents and epoxy monomers, e.g. glycidylmethacrylate. The cross linking agents may be capable of internal cross linking, e.g. diallyl maleate, triallyl cyanurate or crosslinkable, e.g. N-methylolacrylamide.
The acrylate monomer is generally initially present in the form of an emulsion which requires to be stabilised by a protective colloid, and the preferred colloid material is polyvinyl alcohol. There is no criticality in the degree of hydrolysis of polyvinyl alcohol; preferably the degree of hydrolysis is above 70%, and the degree of polymerisation is preferably above 550.
Other protective colloids which can be used include hydroxyethyl cellulose, carboxymethyl cellulose, ethoxylated starch derivatives, polyacrylates, acrylamides, gelatins, alginates, gums and agar. capable of withstanding the heat applied, e.g. up to 200.degree. C., during contact with the polymeric material to be reinforced.


SUMMARY OF THE INVENTION

In one aspect the present invention provides a copolymer emulsion containing from 20% to 70%, preferably 45 to 60%, by weight solids which comprise copolymer particles having a weight mean particle diameter from about 0.05 micron to about 1.5 micron, stabilised by a protective colloid, e.g. polyvinylalcohol, comprising at least about 90% by weight of C1 to C10 alkyl(meth)acrylate monomer to provide a polymerglass transition temperature (Tg) in the range from about 0.degree. C. to about 60.degree. C., preferably from about 20.degree. C. to about to 50.degree. C. The use of the particle sizes quoted allows the preparation of a stable emulsion which is of particular use as a sizing agent suitable for glass fibre; use of larger particles may have a detrimental effect on strand integrity.
The invention thus enables production of acrylate copolymer emulsions suitable for use as a glass fibre sizing agent, which has not hitherto been possible. Acrylates have better properties of heat resistance than materials conventionally used as sizing agents, e.g. vinyl acetate emulsion polymers, and so are better suited to this application

REFERENCES:
patent: 4801643 (1989-01-01), Craig
patent: 4870126 (1989-09-01), Kinson et al.
patent: 4943612 (1990-07-01), Morita et al.
patent: 4960814 (1990-10-01), Wu et al.

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