CA1078096A - Method of making plastic foam laminates and product formed thereby - Google Patents
Method of making plastic foam laminates and product formed therebyInfo
- Publication number
- CA1078096A CA1078096A CA330,452A CA330452A CA1078096A CA 1078096 A CA1078096 A CA 1078096A CA 330452 A CA330452 A CA 330452A CA 1078096 A CA1078096 A CA 1078096A
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- Prior art keywords
- weight
- bis
- vinylphosphonate
- copolymer
- vinyl
- Prior art date
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Abstract
METHOD OF MAKING PLASTIC FOAM LAMINATES
AND PRODUCT FORMED THEREBY
Abstract of the Disclosure Plastic foam laminates are formed by heating a laminate of a base and a plastic film, said film comprising a vinyl chlor-ide-vinyl acetate-bis(hydrocarbyl) vinylphosphonate suspension copolymer and a blowing agent, at a temperature of about 140°C.
to about 160°C. The foam which is formed thereby has a fine, uniform cell quality.
AND PRODUCT FORMED THEREBY
Abstract of the Disclosure Plastic foam laminates are formed by heating a laminate of a base and a plastic film, said film comprising a vinyl chlor-ide-vinyl acetate-bis(hydrocarbyl) vinylphosphonate suspension copolymer and a blowing agent, at a temperature of about 140°C.
to about 160°C. The foam which is formed thereby has a fine, uniform cell quality.
Description
Technical Description of the Invention A method for forming plastic foam laminatPs is described in U.S. Patent No. 2,964,799 to P. E. Roggi et al. wherein a vinyl chloride-vi~yl acetate copolymer mass containing a blow-ing agent can be calendered at 150C.-185C. to fuse the resin and form a thin film on a fabric substrate, and this laminate can then be heated to 190C.-255C. whereby the film expands freely without disruption to form a blown sheet having a contin-uous surface. That patent mentions that use of resins which cal-ender below the 160-185C. temperature range will give a poor foam quality in the final product.
This invention is a method for forming a foam by utiliz-ing a resin formulation which calenders below the range set forth in the Roggi et al. patent, the foam formed thereby, and the resin formulation which is to be used in forming the foam.
.~
. . .
1l~78~)9~ , Thus, in accordance with the present teachings, a method is provided for making a plastic film laminate which comprises forming a laminate of a plastic film on a base, the film comprising a vinyl chloride-vinyl acetate-dis(hydro-carbyl) vinylphosphonate suspension copolymer and a blowing agent.
In accordance with a further embodiment a plastic foam laminate is provided which comprises a base and a plastic foam attached to the base, the foam comprising a suspension co-polymer of vinyl chloride, vinyl acetate and bis(hydrocarbyl) vinyl-phosphonate.
By a further embodiment a plastic laminate is provided which comprises a base, a plastic film attached to the base, the film comprising a suspension copolymer of vinyl chloride, vinyl acetate and bis(hydrocarbyl) vinylphosphonate and blowing agent.
Thus, in accordance with the present teachings, a suspen~ion polymer is provided which comprises from about 80% to about 90% by weight vinyl chloride, from about 2~ to about 15% by weight vinyl acetate, and from about 2% to about 15% by weight of a bis(hydrocarbyl) vinylphosphonate.
The first step in the process of forming the laminate -la-,~j t 1078Q96 CIP of C-4078 is the milling of a solid thermoplastic suspension copolymer which comprises from about 80~ to about 90~ by weight vinyl chloride, about 2~ to about 15~ by weight vinyl acetate, and about 2~ to about 15~ of a bis (hydrocarbyl) vinylphosphonate with an amount of blowing agent which is effective to foam the plastic film in the later heating step~which will be described in greater detail below, and, preferably, with from about 25~
to about 50~ by weight of plasticizer, based on the weight of the resin composition. The amount of plasticizer that is used allows for production of an expandable melt at the heating temperature used in the process. In addition to these components, the composition can also contain conventional amounts of the heat stabilizers, pigments, fillers, colorants or other functional additives known to persons of ordinary skill in the art.
If desired, the resin cmmposition can be easily flame retarded by using phosphate esters, e.g., tricresyl phosphate,
This invention is a method for forming a foam by utiliz-ing a resin formulation which calenders below the range set forth in the Roggi et al. patent, the foam formed thereby, and the resin formulation which is to be used in forming the foam.
.~
. . .
1l~78~)9~ , Thus, in accordance with the present teachings, a method is provided for making a plastic film laminate which comprises forming a laminate of a plastic film on a base, the film comprising a vinyl chloride-vinyl acetate-dis(hydro-carbyl) vinylphosphonate suspension copolymer and a blowing agent.
In accordance with a further embodiment a plastic foam laminate is provided which comprises a base and a plastic foam attached to the base, the foam comprising a suspension co-polymer of vinyl chloride, vinyl acetate and bis(hydrocarbyl) vinyl-phosphonate.
By a further embodiment a plastic laminate is provided which comprises a base, a plastic film attached to the base, the film comprising a suspension copolymer of vinyl chloride, vinyl acetate and bis(hydrocarbyl) vinylphosphonate and blowing agent.
Thus, in accordance with the present teachings, a suspen~ion polymer is provided which comprises from about 80% to about 90% by weight vinyl chloride, from about 2~ to about 15% by weight vinyl acetate, and from about 2% to about 15% by weight of a bis(hydrocarbyl) vinylphosphonate.
The first step in the process of forming the laminate -la-,~j t 1078Q96 CIP of C-4078 is the milling of a solid thermoplastic suspension copolymer which comprises from about 80~ to about 90~ by weight vinyl chloride, about 2~ to about 15~ by weight vinyl acetate, and about 2~ to about 15~ of a bis (hydrocarbyl) vinylphosphonate with an amount of blowing agent which is effective to foam the plastic film in the later heating step~which will be described in greater detail below, and, preferably, with from about 25~
to about 50~ by weight of plasticizer, based on the weight of the resin composition. The amount of plasticizer that is used allows for production of an expandable melt at the heating temperature used in the process. In addition to these components, the composition can also contain conventional amounts of the heat stabilizers, pigments, fillers, colorants or other functional additives known to persons of ordinary skill in the art.
If desired, the resin cmmposition can be easily flame retarded by using phosphate esters, e.g., tricresyl phosphate,
2,3-dibromopropyl phosphate, etc., either alone or in combin-ation with antimony trioxide, hydrated alumina or any other 2Q flame retardant generally used in the plastics industry in amounts conventionally used in flame retarding polyvinyl chloride, e.g., about 2~ to about lo~ of the composition.
The term "bis (hydrocarbyl~ vinylphosphonate" as used herein is intended to encompass vinylphosphonates having the structure:
X O
r ~ OR~
CH2 = C- P~
~ OR~
wherein X is selected from the group consisting of hydrogen, - 1078096 CIP of C-4o78 halogen, cyano, aryl, such as phenyl, Cl-C18 alkyl and o p ,,,OR
OR~
wherein R and R' are hydrocarbyl and substituted hydrocarbyl groups consisting essentially of hydrogen and carbon and con-taining up to about 18 carbon atoms inclusive with the proviso that R and R' may be the same, different or conjoint, i.e., R
~ and R' may form one single radical.
The use in this disclosure of the expression "hydro-carbyl" and "substituted hydrocarbyl" groups refers to the rad-~cals obtained upon the removal of a hydrogen from a hydrocarbon or substituted hydrocarbon group which may be either an aliphat-ic or aromatic group. These hydrocarbyl groups may be substi-tuted with any non-interfering groups, i.e., with any group which toes not ~nterfere wlth the polymerization of the bis-thydrocarbyl) vinylphosphonate. Such sub~tituent groups in-clude, for example, chloro, bromo, fluoro, nitro, hydroxy, sul-ZO fone, ethoxy, methoxy, nitrile, ether, ester and keto groups and the like.
Illustrative of such groups as are represented by R and R' are alkyl or alkenyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, nonyl, pentenyl, and hexenyl groups and all of their respective isomers; cycloalkyl or cycloalkenyl groups, such as cyclopropyl, cyclobutyl, cyclophenyl, cyclohexyl and cyclohexenyl groups and the like; while typical aryl groups represented by R and R' include phenyl, benzyl, phenethyl, tolyl and napthyl groups and the like.
1~ 7809 6 C~P of C-4078 Representative of the above depicted bis(hydrocarbyl) vinylphosphonates which may be used in preparing the fire re-tardant vinyl chloride copolymers of this invention are:
Bis~beta-chloroethyl) vinylphosphonate;
Bis(beta-chloropropyl~ vinylphosphonate;
Bis(beta-chloroethyl) l-methylvinylphosphonate;
Bis(beta-chloroethyl) l-cyanovinylphosphonate;
Bis(beta-chloroethyl~ l-chlorovinylphosphonate;
Bis(beta-chloroethyl) l-phenylvinylphosphonate;
Dimethyl vinylphosphonate;
Diethyl vinylphosphonate;
Bis(omega-chlorobutyl) vinylphosphonate;
Di-n-butyl vinylphosphonate Di-isobutyl vinylphosphonate;
Bis(2-chloroisopropyl) l-methylvinylphosphonate;
Diphenyl vinylphosphonate; and Bis(2,3-dibromopropyl) vinylphosphonate.
It is, however, to be emphasized that it is preferred to employ bis(beta-chloroethyl) vinylphosphonate in preparing the copolymers of this invention since the latter monomer is a commercially available material and is lower in cost than any of the other above listed bis(hydrocarbyl) vinylphosphonates.
The preferred composition of the suspension copolymer f this invention is about 85~ to about 87~ vinyl chloride, about
The term "bis (hydrocarbyl~ vinylphosphonate" as used herein is intended to encompass vinylphosphonates having the structure:
X O
r ~ OR~
CH2 = C- P~
~ OR~
wherein X is selected from the group consisting of hydrogen, - 1078096 CIP of C-4o78 halogen, cyano, aryl, such as phenyl, Cl-C18 alkyl and o p ,,,OR
OR~
wherein R and R' are hydrocarbyl and substituted hydrocarbyl groups consisting essentially of hydrogen and carbon and con-taining up to about 18 carbon atoms inclusive with the proviso that R and R' may be the same, different or conjoint, i.e., R
~ and R' may form one single radical.
The use in this disclosure of the expression "hydro-carbyl" and "substituted hydrocarbyl" groups refers to the rad-~cals obtained upon the removal of a hydrogen from a hydrocarbon or substituted hydrocarbon group which may be either an aliphat-ic or aromatic group. These hydrocarbyl groups may be substi-tuted with any non-interfering groups, i.e., with any group which toes not ~nterfere wlth the polymerization of the bis-thydrocarbyl) vinylphosphonate. Such sub~tituent groups in-clude, for example, chloro, bromo, fluoro, nitro, hydroxy, sul-ZO fone, ethoxy, methoxy, nitrile, ether, ester and keto groups and the like.
Illustrative of such groups as are represented by R and R' are alkyl or alkenyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, nonyl, pentenyl, and hexenyl groups and all of their respective isomers; cycloalkyl or cycloalkenyl groups, such as cyclopropyl, cyclobutyl, cyclophenyl, cyclohexyl and cyclohexenyl groups and the like; while typical aryl groups represented by R and R' include phenyl, benzyl, phenethyl, tolyl and napthyl groups and the like.
1~ 7809 6 C~P of C-4078 Representative of the above depicted bis(hydrocarbyl) vinylphosphonates which may be used in preparing the fire re-tardant vinyl chloride copolymers of this invention are:
Bis~beta-chloroethyl) vinylphosphonate;
Bis(beta-chloropropyl~ vinylphosphonate;
Bis(beta-chloroethyl) l-methylvinylphosphonate;
Bis(beta-chloroethyl) l-cyanovinylphosphonate;
Bis(beta-chloroethyl~ l-chlorovinylphosphonate;
Bis(beta-chloroethyl) l-phenylvinylphosphonate;
Dimethyl vinylphosphonate;
Diethyl vinylphosphonate;
Bis(omega-chlorobutyl) vinylphosphonate;
Di-n-butyl vinylphosphonate Di-isobutyl vinylphosphonate;
Bis(2-chloroisopropyl) l-methylvinylphosphonate;
Diphenyl vinylphosphonate; and Bis(2,3-dibromopropyl) vinylphosphonate.
It is, however, to be emphasized that it is preferred to employ bis(beta-chloroethyl) vinylphosphonate in preparing the copolymers of this invention since the latter monomer is a commercially available material and is lower in cost than any of the other above listed bis(hydrocarbyl) vinylphosphonates.
The preferred composition of the suspension copolymer f this invention is about 85~ to about 87~ vinyl chloride, about
3~ toabout 8~ vinyl acetate and about 5~ to about 7~ bis (beta-chloroethyl) vinylphGsphonate. Any of the copolymers suitable for use in the present invention are formed by subjecting the CIP of C-4078 1C~78096 foregoing monomers to conventional suspension polymerization procedures which are well known to persons of ordinary skill in the art. Typically, such procedures entail the use of from about o.o510 to about 1~, by weight of the monomers, of a sus-pending agent, e.g., methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, talc, clay, polyvinyl alcohol, gelatine or the like, with from about 0.2~
to about l.o~, by weight of the monomers, of a monomer-soluble initiator, e.g., azobisisobutyronitrile, lauroyl peroxide, lo benzoyl peroxide or isopropylperoxy dicarbonate, in an aqueous medium containing said monomers. The polymerization is con-ducted at about 45C. to about 75C. for a period of about 2 to 12 hours with agitation being applied throughout ~he reaction.
The relative viscosity of the copolymers (1~ in cyclohexanone at 25C.) should range from about 1.7 to about 2.7.
The blowing agent which is used is present in an effec-tive amount, e.g., preferably ranging from about 1~ to about 20 by weight of the copolymer, most preferably from about 7.5% to about lo~ by weight, and is one which decomposes at a tempera-ture of from about 140 to about 160C. The preferred blowing agent is 4,4' oxybis(benzenesulfonyl hydrazide) which is avail-able from Uniroyal Chemical Div., under the trademark "Celogen OT".
The milling may be accomplished in an internal mixer, open roll mill, or both, at a temperature which is less than that required to decompose the blowing agent. The milled com-position containing the copolymer is a unitary, solid mass, CIP of C-4078 1~78096 rather than particulate, and the composition is non-flowing and self-supporting at ordinary temperatures. The amount of plasticizer used should be from about 25 to about 50~, by weight, based on the weight of copolymer. Any conventional polyvinyl chloride plasticizer can be used. Conventional stabilizers, colorants, antioxidants, lubricants and other additives can also be included in conventional amounts in the composition.
The next step of the process involves the calendering of the milled copolymer-containing composition onto a suitable base. Flexible bases, such as a fabric base, are preferred.
The calendering is accomplished by using a conventional cal-end~r, e.g., a three or four roll calender, at a temperature sufficiently elevated to bring about substantial fusion of the resin so that a coherent, uniform film , is formed. The temperature should be about lloC. to about 125C., preferably about 115 to about 125C. These temperatures are insufEicient to cause decomposition of the blowing agent contained in the composition. The calendering step forms a film having a thickness of from about lO to about 120 mils on the base. This product can be wound up into a roll, or transported or stored in any other convenient form, for an indefinite period of time.
Alter~atively, the copolymer composition may first be calendered into a cohesive, unsupported film or sheet which is then combined with the flexible base to form a laminated con-struction by the use of an adhesive or by ~he application of heat and pressure. Typical adhesives are plastisols, latexes, solutions, dispersions or hot melts which are suitably form-~ 809 6 CIP of C-4078 ulated as is well known to those of ordinary skill in ehe art.
The adhesive may be applied to the side to be laminated on either the flexi~e base or the unsupported film or sheet. The two components of the construction are then contacte~ with each other, and the adhesive is allowed to dry or cure thereby form-ing a permanently bonded laminate. If practical, the copolymer film or sheet may be placed on the flexible substrate and lam-inated thereto by the use of heat and pressure.
After the calendered base and copoly,~er composition is formed, it is then heated to a temperature of from about 140 C~
to about 160C. for a period of from about 5 to about 15 min.
to decompose the blowing agent and thereby foam the compostion containing the copolymer and blowing agents.
The following Examples illustrate the present invention:
This illustrates formation of a suspension copolymer suitable for use in forming the laminates of the present in-vention.
Deionized water (52 lbsq 13 oz.) and 32 grams of Metho-cel suspending agent solution were charged into a lo gallon re-actor. Vinyl acetate (2 lbs.~ and bis (beta-chloroethyl) vinyl-phosphonate (1 lb. 11 oz.) were added followed by 5 grams of azobisisobutyronitrile catal~st (Vazo-52). The manhole of the reactor was closed, vacuum was twice applied, and the reactor was purged with nitrogen. The vinyl chloride monomer (24 lbs 8 oz.) was then charged into the reactor, and the mixture was stirred at 496 rpm. for about 30 minutes. The reactor was heated to 52C. and was maintained at this temperature until th~e pres-sure dropped by 30 psi from the levels noted while the reaction 1~78096 CIP of C-4078 was initiated. At this point lo grams of 2,6-di-tert-butyl-4-methylphenol (IonoL) was added. The product was recovered by centrifuging in the presence of filter paper and was dried in an oven dryer.
A composition was formed by milling the ingredients listed in the Table for seven minutes (front roll: 245F., 30 feet/min.; back roll: 250F., 42 feet/min.):
AMOUNT
lo INGREDIENTS (Parts by Weight) 87~ vinyl chloride: 7 vinyl acetate: 6~ bis (beta-chloroethyl)vinyl-phosphonate copolymer* loo Dioctyl Phthalate 40 Butyl Benzyl Phthalate 15 Epoxidized Soya~fan oil 5 Stabilizer (ABC~) 3 Filler (CaC03) lo Pigment (TiO2) , 2 Lubricant (Stearic Acid) 2.5 Celogen-OT (4,4'-oxybis benzene sulfonyl hydrazide~ 8 *Relative visc08ity: 2.17,made as described in Example 1.
Another formulation was milled according to Example 2 and contained the following:
AMOUNT
INGREDIENTS (Parts By Weight) Copolymer of Example 1 loo Dioctyl Phthalate 60 Butyl Benzyl Phthalate 20 Epoxidized Soyabean Oil 5 Stabilizer (ABC-2) 3 Filler (CaC03) lo Pigment (TiO2) 2 Lubricant (Stearic Acid) 2.5 Celogen-OT(4,4'-oxybis benzene sulfonyl hydrazide) 8 ~078096 CIP of C-4o78 These examples show use of polymer compositions falling out-side the scope of the present invention and use of a blowing agent which does not decompose in the range of 140C,-160C.
All milling conditions are the same as in Example 1.
AMOUNT
INGREDIENTS ~Parts By Weight) 87~ vinyl chloride: 7 vinyl acetate: 6~ bis (beta-chloroethyl)vinyl-phosphonate copolymer* 100 Dioctyl Phthalate 40 Butyl Benzyl Phthalate 15 Epoxidized Soyabean Oil 5 Stabilizer (ABC-2) 3 Filler (CaC03) lo Pigment (TiO2) 2 Lubriant (Stearic Acid~ 2.5 R-80~(Diisopropyl Azodiformate) 8 ~Relative Vi8cosity: 2.17 AMOUNT
INGREDIENTS (Parts By Weight~
85.5~ vinyl chloride: 10.7 (beta-chloroethyl~ vinyl-phosphonate: 3.8~ propylene* loo Dioctyl Phthalate 25 Butyl benzyl phthalate 15 3 Epoxidized Soyabean Oil 5 Stabilizer (ABC-2) 3 Filler (CaC03) lo Pigment (Tio23 2 Lubricant (Stearic Acid) 2.5 Celogen-OT (4,4'-oxybis benzenesulfonyl hydrazide) 8 ~This copolymer at 60 parts per hundred plasticizer was too soft and could not be milled.
1~7809~ CIP of C-4078 AMOUNT
INGREDIENTS (Parts By Weight) 90% vinyl chloride: lo~ bis (beta-chloroethyl) vinyl-phosphonate* loO
Dioctyl Phthalate 40 Butyl benzyl phthalate 15 Epoxidized Soyabean Oil 5 lo Stabilizer (ABC-2) 3 Filler (CaC03) lO
Pigment (TiO2) 2 Lubricant (Stearic acid) 2.5 Celogen-OT(4,4'oxybis benzene-sulfonyl hydrazide) 8 ~Relative Viscosity: 2.5 Each of the five compositions in Examples 2-6 was lam-inated onto a fabric in a two roll mill. The laminated film was expanded by heating in a circulatory oven for five minutes at 320F. The table sets forth the pre-expansion and post ex-pansion characteristics.
PRE-EXPANSION POST-EXPANSION BLOW-UP
THICKNESS THICKNESS RATE* CELL
COMPOSITION(MILS) (MILS) (~) QUALITY
Ex. 2 80 205 300 E'ine &
Uniform Ex. 3 63 280 600 Fine ~
Uniform Ex. 4 74 135 210 Coarse Ex. 5 99 179 200 Coarse Ex. 6 98 187 210 Coarse ~Corrected for a fabric thickness of 20 mil.
to about l.o~, by weight of the monomers, of a monomer-soluble initiator, e.g., azobisisobutyronitrile, lauroyl peroxide, lo benzoyl peroxide or isopropylperoxy dicarbonate, in an aqueous medium containing said monomers. The polymerization is con-ducted at about 45C. to about 75C. for a period of about 2 to 12 hours with agitation being applied throughout ~he reaction.
The relative viscosity of the copolymers (1~ in cyclohexanone at 25C.) should range from about 1.7 to about 2.7.
The blowing agent which is used is present in an effec-tive amount, e.g., preferably ranging from about 1~ to about 20 by weight of the copolymer, most preferably from about 7.5% to about lo~ by weight, and is one which decomposes at a tempera-ture of from about 140 to about 160C. The preferred blowing agent is 4,4' oxybis(benzenesulfonyl hydrazide) which is avail-able from Uniroyal Chemical Div., under the trademark "Celogen OT".
The milling may be accomplished in an internal mixer, open roll mill, or both, at a temperature which is less than that required to decompose the blowing agent. The milled com-position containing the copolymer is a unitary, solid mass, CIP of C-4078 1~78096 rather than particulate, and the composition is non-flowing and self-supporting at ordinary temperatures. The amount of plasticizer used should be from about 25 to about 50~, by weight, based on the weight of copolymer. Any conventional polyvinyl chloride plasticizer can be used. Conventional stabilizers, colorants, antioxidants, lubricants and other additives can also be included in conventional amounts in the composition.
The next step of the process involves the calendering of the milled copolymer-containing composition onto a suitable base. Flexible bases, such as a fabric base, are preferred.
The calendering is accomplished by using a conventional cal-end~r, e.g., a three or four roll calender, at a temperature sufficiently elevated to bring about substantial fusion of the resin so that a coherent, uniform film , is formed. The temperature should be about lloC. to about 125C., preferably about 115 to about 125C. These temperatures are insufEicient to cause decomposition of the blowing agent contained in the composition. The calendering step forms a film having a thickness of from about lO to about 120 mils on the base. This product can be wound up into a roll, or transported or stored in any other convenient form, for an indefinite period of time.
Alter~atively, the copolymer composition may first be calendered into a cohesive, unsupported film or sheet which is then combined with the flexible base to form a laminated con-struction by the use of an adhesive or by ~he application of heat and pressure. Typical adhesives are plastisols, latexes, solutions, dispersions or hot melts which are suitably form-~ 809 6 CIP of C-4078 ulated as is well known to those of ordinary skill in ehe art.
The adhesive may be applied to the side to be laminated on either the flexi~e base or the unsupported film or sheet. The two components of the construction are then contacte~ with each other, and the adhesive is allowed to dry or cure thereby form-ing a permanently bonded laminate. If practical, the copolymer film or sheet may be placed on the flexible substrate and lam-inated thereto by the use of heat and pressure.
After the calendered base and copoly,~er composition is formed, it is then heated to a temperature of from about 140 C~
to about 160C. for a period of from about 5 to about 15 min.
to decompose the blowing agent and thereby foam the compostion containing the copolymer and blowing agents.
The following Examples illustrate the present invention:
This illustrates formation of a suspension copolymer suitable for use in forming the laminates of the present in-vention.
Deionized water (52 lbsq 13 oz.) and 32 grams of Metho-cel suspending agent solution were charged into a lo gallon re-actor. Vinyl acetate (2 lbs.~ and bis (beta-chloroethyl) vinyl-phosphonate (1 lb. 11 oz.) were added followed by 5 grams of azobisisobutyronitrile catal~st (Vazo-52). The manhole of the reactor was closed, vacuum was twice applied, and the reactor was purged with nitrogen. The vinyl chloride monomer (24 lbs 8 oz.) was then charged into the reactor, and the mixture was stirred at 496 rpm. for about 30 minutes. The reactor was heated to 52C. and was maintained at this temperature until th~e pres-sure dropped by 30 psi from the levels noted while the reaction 1~78096 CIP of C-4078 was initiated. At this point lo grams of 2,6-di-tert-butyl-4-methylphenol (IonoL) was added. The product was recovered by centrifuging in the presence of filter paper and was dried in an oven dryer.
A composition was formed by milling the ingredients listed in the Table for seven minutes (front roll: 245F., 30 feet/min.; back roll: 250F., 42 feet/min.):
AMOUNT
lo INGREDIENTS (Parts by Weight) 87~ vinyl chloride: 7 vinyl acetate: 6~ bis (beta-chloroethyl)vinyl-phosphonate copolymer* loo Dioctyl Phthalate 40 Butyl Benzyl Phthalate 15 Epoxidized Soya~fan oil 5 Stabilizer (ABC~) 3 Filler (CaC03) lo Pigment (TiO2) , 2 Lubricant (Stearic Acid) 2.5 Celogen-OT (4,4'-oxybis benzene sulfonyl hydrazide~ 8 *Relative visc08ity: 2.17,made as described in Example 1.
Another formulation was milled according to Example 2 and contained the following:
AMOUNT
INGREDIENTS (Parts By Weight) Copolymer of Example 1 loo Dioctyl Phthalate 60 Butyl Benzyl Phthalate 20 Epoxidized Soyabean Oil 5 Stabilizer (ABC-2) 3 Filler (CaC03) lo Pigment (TiO2) 2 Lubricant (Stearic Acid) 2.5 Celogen-OT(4,4'-oxybis benzene sulfonyl hydrazide) 8 ~078096 CIP of C-4o78 These examples show use of polymer compositions falling out-side the scope of the present invention and use of a blowing agent which does not decompose in the range of 140C,-160C.
All milling conditions are the same as in Example 1.
AMOUNT
INGREDIENTS ~Parts By Weight) 87~ vinyl chloride: 7 vinyl acetate: 6~ bis (beta-chloroethyl)vinyl-phosphonate copolymer* 100 Dioctyl Phthalate 40 Butyl Benzyl Phthalate 15 Epoxidized Soyabean Oil 5 Stabilizer (ABC-2) 3 Filler (CaC03) lo Pigment (TiO2) 2 Lubriant (Stearic Acid~ 2.5 R-80~(Diisopropyl Azodiformate) 8 ~Relative Vi8cosity: 2.17 AMOUNT
INGREDIENTS (Parts By Weight~
85.5~ vinyl chloride: 10.7 (beta-chloroethyl~ vinyl-phosphonate: 3.8~ propylene* loo Dioctyl Phthalate 25 Butyl benzyl phthalate 15 3 Epoxidized Soyabean Oil 5 Stabilizer (ABC-2) 3 Filler (CaC03) lo Pigment (Tio23 2 Lubricant (Stearic Acid) 2.5 Celogen-OT (4,4'-oxybis benzenesulfonyl hydrazide) 8 ~This copolymer at 60 parts per hundred plasticizer was too soft and could not be milled.
1~7809~ CIP of C-4078 AMOUNT
INGREDIENTS (Parts By Weight) 90% vinyl chloride: lo~ bis (beta-chloroethyl) vinyl-phosphonate* loO
Dioctyl Phthalate 40 Butyl benzyl phthalate 15 Epoxidized Soyabean Oil 5 lo Stabilizer (ABC-2) 3 Filler (CaC03) lO
Pigment (TiO2) 2 Lubricant (Stearic acid) 2.5 Celogen-OT(4,4'oxybis benzene-sulfonyl hydrazide) 8 ~Relative Viscosity: 2.5 Each of the five compositions in Examples 2-6 was lam-inated onto a fabric in a two roll mill. The laminated film was expanded by heating in a circulatory oven for five minutes at 320F. The table sets forth the pre-expansion and post ex-pansion characteristics.
PRE-EXPANSION POST-EXPANSION BLOW-UP
THICKNESS THICKNESS RATE* CELL
COMPOSITION(MILS) (MILS) (~) QUALITY
Ex. 2 80 205 300 E'ine &
Uniform Ex. 3 63 280 600 Fine ~
Uniform Ex. 4 74 135 210 Coarse Ex. 5 99 179 200 Coarse Ex. 6 98 187 210 Coarse ~Corrected for a fabric thickness of 20 mil.
Claims (4)
1. A suspension copolymer which comprises from about 80% to about 90%. by weight, vinyl chloride, from about 2% to about 15%, by weight, vinyl acetate, and from about 2% to about 15%, by weight, of a bis (hydrocarbyl) vinylphosphonate.
2. A copolymer as claimed in Claim 1 wherein the vinyl chloride comprises about 85% to about 87%, by weight, the vinyl acetate comprises about 3% to about 8%, by weight, and the vinylphosphonate content comprises about 5% to about 7% by weight.
3. A copolymer as claimed in Claim 1 wherein the vinyl chloride comprises about 87%, by weight, the vinyl acetate comprises about 7%, by weight, and the vinylphos-phonate comprises about 6%, by weight.
4. A copolymer as claimed in Claim 1 wherein the vinylphosphonate is bis (beta-chloroethyl) vinylphosphonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA330,452A CA1078096A (en) | 1974-08-09 | 1979-06-25 | Method of making plastic foam laminates and product formed thereby |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49622874A | 1974-08-09 | 1974-08-09 | |
| US05/588,103 US3983294A (en) | 1974-08-09 | 1975-06-23 | Method of making plastic foam laminates and product formed thereby |
| CA232,681A CA1071991A (en) | 1974-08-09 | 1975-08-01 | Method of making plastic foam laminates and product formed thereby |
| CA330,452A CA1078096A (en) | 1974-08-09 | 1979-06-25 | Method of making plastic foam laminates and product formed thereby |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1078096A true CA1078096A (en) | 1980-05-20 |
Family
ID=27425857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA330,452A Expired CA1078096A (en) | 1974-08-09 | 1979-06-25 | Method of making plastic foam laminates and product formed thereby |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1078096A (en) |
-
1979
- 1979-06-25 CA CA330,452A patent/CA1078096A/en not_active Expired
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |