Methods for improving chemical and flame resistance with multi-functional photoactive additives
View Patent ↗Polymeric blends having improved flame retardance properties and good ductility at low temperatures are disclosed. The blend is formed from (A) a photoactive additive that is a cross-linkable polycarbonate resin containing a photoactive group derived from a dihydroxybenzophenone; and (B) a polymer resin which is different from the photoactive additive. The additive can be a compound, oligomer, or polymer. When exposed to ultraviolet light, crosslinking will occur between the photoactive additive and the polymer resin, enhancing the chemical resistance and flame retardance while maintaining ductility.
1. A polymeric blend, comprising:
a photoactive additive that is a cross-linkable polycarbonate resin containing a photoactive group derived from a dihydroxybenzophenone which is a dihydroxyphenyl-phenylmethanone, a bis(hydroxyphenyl)methanone, a 1-dihydroxyphenyl-2-phenylethane-1,2-dione, a 1,2-bis(hydroxyphenyl)ethane-1,2-dione, a 1-(dihydroxyphenyl)-2-hydrocaroxy-2-phenylethanone, a 1,2-bis(hydroxyphenyl)-2-hydrocarboxy-ethanone, a dihydroxydibenzo[1,3-e:1′,2′-f][7]annulen-11-one, or a dihydroxythioxanthen-9-one;
a polymer resin which is different from the photoactive additive; and
a flame retardant, wherein the flame retardant is potassium perfluorobutane sulfonate (Rimar salt), potassium diphenyl sulfone-3-sulfonate (KSS), or a combination thereof; and
wherein the photoactive additive does not contain units derived from a bisphenolpolydiorganosiloxane and is formed from a reaction comprising:
the dihydroxybenzophenone;
a diol chain extender other than the bisphenolpolydiorganosiloxane;
a first linker moiety comprising a plurality of linking groups, wherein each linking group reacts with the hydroxyl groups of the dihydroxybenzophenone and the diol chain extender; and
an end-capping agent;
wherein the molar ratio of the dihydroxybenzophenone to the first linker moiety is from 1:2 to 1:200 prior to UV exposure; and
the weight ratio of the photoactive additive to the polymer resin is from about 10:90 to about 15:85.
2. The blend of claim 1 , wherein the polymer resin is a polyester, a polyestercarbonate, a bisphenol-A homopolycarbonate, a polycarbonate copolymer, a tetrabromo-bisphenol A polycarbonate copolymer, a polysiloxane-co-bisphenol-A polycarbonate, a polyesteramide, a polyimide, a polyetherimide, a polyamideimide, a polyether, a polyethersulfone, a polyepoxide, a polylactide, a polylactic acid (PLA), or any combination thereof.
3. The blend of claim 1 , wherein the polymer resin is a vinyl polymer, a rubber-modified graft copolymer, an acrylic polymer, polyacrylonitrile, a polystyrene, a polyolefin, a polyester, a polyesteramide, a polysiloxane, a polyurethane, a polyamide, a polyamideimide, a polysulfone, a polyepoxide, a polyether, a polyimide, a polyetherimide, a polyphenylene ether, a polyphenylene sulfide, a polyether ketone, a polyether ether ketone, an acrylonitrile-butadiene-styrene (ABS) resin, an acrylic-styrene-acrylonitrile (ASA) resin, a polyethersulfone, a polyphenylsulfone, a poly(alkenylaromatic) polymer, a polybutadiene, a polyacetal, a polycarbonate, a polyphenylene ether, an ethylene-vinyl acetate copolymer, a polyvinyl acetate, a liquid crystal polymer, an ethylenetetrafluoroethylene copolymer, an aromatic polyester, a polyvinyl fluoride, a polyvinylidene fluoride, a polyvinylidene chloride, tetrafluoroethylene, a polylactide, a polylactic acid (PLA), a polycarbonate-polyorganosiloxane block copolymer, or a copolymer comprising: (i) an aromatic ester, (ii) an estercarbonate, and (iii) carbonate repeat units.
4. The blend of claim 1 , wherein the polymer resin is a homopolycarbonate, a copolycarbonate, a polycarbonate-polysiloxane copolymer, a polyester-polycarbonate, or a p-cumyl phenol capped poly(isophthalate-terephthalate-resorcinol ester)-co-(bisphenol-A carbonate) copolymer.
5. The blend of claim 1 , wherein the polymer resin is a p-cumyl phenol capped poly(isophthalate-terephthalate-resorcinol ester)-co-(bisphenol-A carbonate) polymer or a polycarbonate-polysiloxane copolymer having a polysiloxane content from 0.4 wt % to 25 wt %.
6. The blend of claim 5 , wherein the polycarbonate-polysiloxane copolymer is a siloxane block co-polycarbonate comprising from about 6 wt % siloxane (±10%) to about 20 wt % siloxane (±10%), and having a siloxane chain length of 10 to 200.
7. The blend of claim 1 , wherein the polymer resin is a polyphosphonate polymer, a polyphosphonate copolymer, or a poly(polyphosphonate)-co-(BPA carbonate) copolymer.
8. The blend of claim 1 , wherein the polymer resin is selected from the group consisting of a polycarbonate-polysiloxane copolymer; a polycarbonate resin having an aliphatic chain containing at least two carbon atoms as a repeating unit in the polymer backbone; an ethylene-acrylic ester-glycidyl acrylate terpolymer; a copolyester polymer; a bisphenol-A homopolycarbonate; a polystyrene polymer; a poly(methyl methacrylate) polymer; a thermoplastic polyester; a polybutylene terephthalate polymer; a methyl methacrylate-butadiene-styrene copolymer; an acrylonitrile-butadiene-styrene copolymer; a dimethyl bisphenol cyclohexane-co-bisphenol-A copolymer; a polyetherimide; a polyethersulfone; and a copolycarbonate of bisphenol-A and 1, 1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane).
9. The blend of claim 1 , wherein the end-capping agent is selected from the group consisting of phenol, p-t-butylphenol, p-cumylphenol, octylphenol, and p-cyanophenol.
10. The blend of claim 1 , wherein the photoactive additive has a weight average molecular weight of 15,000 or greater prior to UV exposure.
11. The blend of claim 1 , wherein the photoactive additive is a cross-linkable polycarbonate resin having a weight-average molecular weight of between 17,000 and 80,000 Daltons, as measured by GPC using a UV-VIS detector and polycarbonate standards prior to UV exposure.
12. The blend of claim 1 , wherein the cross-linkable polycarbonate resin has a polydispersity index (PDI) of between 2.0 and 3.0 as measured by GPC using a UV-VIS detector and polycarbonate standards prior to UV exposure.
13. The blend of claim 1 , wherein the cross-linkable polycarbonate resin has a melt flow rate of about 1 to about 40 g/10 min at 300° C/1.2 kg/360 sec dwell.
14. The additive of claim 1 , wherein the photoactive additive is a cross-linkable polycarbonate resin having a melt flow rate of about 1 to about 40 g/10 min at 300° C/1.2 kg/360 sec dwell, and a plaque formed from the cross-linkable polycarbonate resin can achieve UL94 5VA performance at a thickness of 1.5 mm (±10%) after UV irradiation of 36.0 J/cm 2 UVA.
15. The blend of claim 1 , wherein the flame retardant is present in an amount of about 0.06 wt % to about 0.08 wt %.
16. The blend of claim 1 , further comprising a heat stabilizer and a mold release agent.
17. The blend of claim 1 , further comprising an UV stabilizer, colorant, flame retardant, heat stabilizer, plasticizer, lubricant, mold release agent, filler, reinforcing agent, antioxidant agent, antistatic agent, blowing agent, or radiation stabilizer.
18. The blend of claim 1 , wherein the polymer resin is a polycarbonate-polysiloxane copolymer having a siloxane content of from about 4 wt% to about 8 wt %, based on the total weight of the blend.
19. The blend of claim 1 , wherein a plaque formed from the blend achieves a UL94 5VA rating at a thickness of 1.5 mm (±10%).
20. The blend of claim 1 , wherein the polymer resin is a bisphenol-A homopolycarbonate; a copolycarbonate of bisphenol-A and 1, 1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane); a copolyester polymer; a copolymer comprising: (i) an aromatic ester, (ii) an estercarbonate, and (iii) carbonate repeat units; a dimethyl bisphenol cyclohexane-co-bisphenol-A copolymer; a homopolycarbonate; a liquid crystal polymer; a methyl methacrylate-butadiene-styrene copolymer; a p-cumyl phenol capped poly(isophthalate-terephthalate-resorcinol ester)-co-(bisphenol-A carbonate) polymer; a poly(alkenylaromatic) polymer; a poly(methyl methacrylate) polymer; a poly(polyphosphonate)-co-(BPA carbonate) copolymer; a polyacetal; a polyamide; a polyamideimide; a polybutadiene; a polybutylene terephthalate polymer; a polyepoxide; a polyester; a polyesteramide; a polyestercarbonate; a polyester-polycarbonate; a polyether ether ketone; a polyether ketone; a polyether; a polyetherimide; a polyethersulfone; a polyimide; a polylactic acid (PLA); a polylactide; a polyolefin; a polyphenylene ether; a polyphenylene sulfide; a polyphenylsulfone; a polyphosphonate copolymer; a polyphosphonate polymer; a polysulfone; a polyurethane; a polyvinyl acetate; a polyvinyl fluoride; a polyvinylidene chloride; a polyvinylidene fluoride; a tetrabromo-bisphenol A polycarbonate copolymer; a thermoplastic polyester; an acrylic polymer; an aromatic polyester; an ethylene-acrylic ester-glycidyl acrylate terpolymer; an ethylene-tetrafluoroethylene copolymer; an ethylene-vinyl acetate copolymer; polyacrylonitrile; tetrafluoroethylene; or any combination thereof.