CN1097773A - Controllable light-light biodegradation polystyrene foam resin and preparation method thereof - Google Patents
Controllable light-light biodegradation polystyrene foam resin and preparation method thereof Download PDFInfo
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- CN1097773A CN1097773A CN 94105049 CN94105049A CN1097773A CN 1097773 A CN1097773 A CN 1097773A CN 94105049 CN94105049 CN 94105049 CN 94105049 A CN94105049 A CN 94105049A CN 1097773 A CN1097773 A CN 1097773A
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Abstract
The present invention relates to dose the polystyrene foam resin of the inorganic photosensitizers of Fe-Ni series, polystyrene can be by microbial attack after handling through photodegradation.Utilize conventional foamed polystyrene equipment, can produce this controllable light-biodegradation type polystyrene foam resin that has.This method production technique is easy, and cost is low, raw material is easy to get.The polystyrene foam resin that uses this method production can be degraded into bead voluntarily by the effect of photodegradation and soil microorganisms after finishing use, finally become CO
2And H
2O.
Description
The present invention relates to controllable biologically degraded foamex and preparation method thereof, this resin is made up of polystyrene and photosensitizers etc.
In recent years, along with porous plastics the widening day by day of use range in daily life and industrial production, the pollution problem increasingly significant that porous plastics brings, plastic foam rubbish proportion in rubbish increases day by day, the handling problem of this type of rubbish makes environmental protection circle headache-burning can bring obnoxious flavour, enter the ocean and can be eaten by mistake by biology again, influence the eubiosis.Some countries of Northern Europe have just passed through relevant restriction or have banned use of the rules of non-degradative plastics goods as far back as nineteen ninety to this early consciously.At present, this way is accepted by most countries.Similar regulation or policy have been formulated in succession.
Current expandability rigid plastics mainly contains two and produces route: one is as raw material with Polyurethane; Article one, be to be raw material with polystyrene.And these two lines all can not be degraded well, cause public hazards very big.
The unique polyvinyl alcohol that can degrade smoothly, its immersion property is very strong, has a large amount of water moleculess outwards to discharge, and when the wrapping material as household electrical appliance used, it easily made product make moist, and influences quality.
Because wrapping material can not be degraded, contaminate environment causes the drawback on the electric equipment products packing.USP.3,917,545 disclose a kind of photodegradable styrene polymer foam, wherein contain hydro carbons photosensitizers such as fluorenes, acenaphthene, dihydroanthracene etc.GB1,385,497 disclose a kind of photodegradable polystyrene foam, have wherein used organic photosensitive agent such as benzophenone, anthrone, anthraquinone etc.US4,076,655 disclose a kind of photodegradable random isotactic polystyrene composition (comprising Polystyrene Film and polystyrene foam), wherein contain photodegradation promotor, contain the organic compound of carbonyl as bitter almond oil camphor, benzophenone etc., used the acetylacetonate of carboxylate metal salt and iron cobalt in addition.All used more organic compound class photosensitizers in these documents, this class photosensitizers has bigger toxicity, easily environment is polluted.In addition, this class photosensitizers is uncontrollable when promoting polymer degradation, (does not wish during this period of time to degrade) in the use of this foam article and just Degradation may take place, and will certainly influence the performance of foam article like this.
In order to respond the requirement of international environmental protection organization to Nonpoisonous, non-environmental-pollution degraded bubble wrap product, the present inventor begins trial-production in August, 93.In trial-manufacturing process, explore a degraded type expandability hard packing material-controllable biologically degraded polystyrene foam resin.The research of these wrapping material has successfully solved the problem that domestic and international all electric equipment products can not be degraded and bring because of styroform package material.After these wrapping material used up, kiss the earth was accepted ultraviolet irradiation, can be controlled in inductive phase 30-120 days, after inductive phase, can degrade quickly, and under field conditions (factors), resolve into beads, perhaps be vulnerable to the erosion of microorganism, perhaps resolve into carbonic acid gas and water.
The present invention has adopted the inorganic photosensitizers of Fe-Ni series of may command degraded inductive phase first, make an addition in the expandable polystyrene bead, foaming method by routine prepares controllable biologically degraded polystyrene foam resin, and this foamy Degradation can be controlled within the preset time and takes place, that is to say, this foam can be degraded rapidly after being abandoned in the usage period of finishing regulation, and degraded product can be assimilated by mushrooms such as mould, fungies.
Expandable polystyrene bead (hereinafter to be referred as EPS) is to add lower boiling fat hydrocarbon or halogenated aliphatic hydrocarbon class whipping agent in the suspension method polystyrene bead, makes expandable bead under certain temperature, pressure.Expandable polystyrene bead adds photosensitizers and carries out pre-frothing after placing all dryings, again with the pre-expanded beads maturation process, places the moulding of the interior feeding of porous mold steam heating promptly to make the degraded type polystyrene foamed plastics.Also photosensitizers and whipping agent can be added simultaneously.
The polystyrene that the present invention is used to foam can be the polystyrene of any currently known methods preparation, the bead polystyrene of preferred suspension processes preparation, and molecular weight is greatly about 5.5-6 ten thousand.
Whipping agent is gasiform or the compound that can produce gas when being heated.Preferred blowing agent is the lower aliphatic hydro carbons, and as methane, ethane, propane, butane, pentane, Trimethylmethane, heptane, hexanaphthene etc. and their halo derivatives class, as chloroparaffin, the boiling point of these compounds is all lower.In when foaming, can use in these compounds one or more.The consumption of whipping agent is 6-12 part/per 100 parts of polystyrene.(wherein umber all by weight, Hereinafter the same).
Photosensitizers used in the present invention mainly comprises the mixture of iron cpd and/or Zirconium oxide and nickel compound.Iron cpd for example is that the inorganic salt of iron are (as FeCl
3Deng) and the oxide compound of iron (as Fe
2O
3, Fe
3O
4, FeO) and the organic salt of iron (as iron stearate and N, N-two C
1-30Alkyl dithiocarbamic acid iron etc.), preferred Fe
2O
3And Fe
3O
4The preferred ZrO of Zirconium oxide
2Nickel compound is an organic nickel, as C
1-80Alkyl nickel, C
1-80Alkoxyl group nickel and C
1-80Alkylthio nickel etc., preferred alkyl nickel, for example methyl nickel, ethyl nickel, propyl group nickel, butyl nickel, amyl group nickel, decyl nickel, tetracosyl nickel, isopentyl nickel etc.Most preferably two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) nickel, 2,2 '-thiobis (uncle's 4-octyl phenol oxygen base) nickel-n-Butyl Amine 99 complex compound, 2,2 '-thiobis (uncle's 4-octyl phenol oxygen base) nickel-2 ethyl hexylamine complex compound, 2,2 '-thiobis (uncle's 4-octyl phenol oxygen base) nickel, and N, N-two C
1-30Alkyl dithiocarbamic acid nickel and analogue thereof.In the photosensitizers of making, the content ratio of iron and nickel be 1: 0.1 to 1: 0.95(is by weight), total consumption of photosensitizers is 1-12 part/per 100 parts of polystyrene.It will also be appreciated that the inorganic and organic salt that uses nickel, as nickelous chloride, nickelous nitrate, nickel stearate, also is within the scope of the invention.
The tensio-active agent that the present invention uses has three types of anionic, cationic and non-ionic types, preferably uses aniorfic surfactant, sodium lauryl sulphate for example, Sodium dodecylbenzene sulfonate etc.The consumption of tensio-active agent is 1-8 part/per 100 parts of polystyrene.
The present invention has used dispersion medium when preparation EPS, this dispersion medium can be water or other inert solvent, preferably makes water.The consumption of dispersion medium is 140-240 part/per 100 parts of polystyrene.
The present invention also adds fire retardant, linking agent, oxidation inhibitor, UV light absorber etc. in preparation EPS, can prepare the controllable biologically degraded polystyrene foam resin of flame retardant type.
The fire retardant that the present invention uses can be an additive flame retardant, also can be reactive flame retardant, preferred fire retardant be weisspiessglanz, pentabromo-ethylbenzene, pentabromochlorocyclohexane, tetrachloroethane, tetrabromoethane, tribromo phenyl allyl ether, tetrabromo-bisphenol-allyl ethers etc.The consumption of fire retardant is 2-5 part/per 100 parts of polystyrene.
The preferred organic peroxide of linking agent that the present invention uses, dicumyl peroxide for example, benzoyl peroxide, α, α-two (tert-butyl peroxy base) diisopropylbenzene(DIPB), peroxidized t-butyl perbenzoate etc.The consumption of linking agent is 0.2-0.9 part/per 100 parts of polystyrene.
The preferred phenolic compound of oxidation inhibitor that the present invention uses, 1-hydroxy-3-methyl-4-isopropyl benzene for example, 2,6 ditertiary butyl p cresol etc.The consumption of oxidation inhibitor is 0.2-0.6 part/per 100 parts of polystyrene.
The spendable UV light absorber of the present invention in dosing resin after, remove to possess in the usage period, to have and to absorb the UV-light inhibition or weaken photodegradation, but after the usage period, group wherein will become again the effective photosensitizers of high-molecular optical DeR, and help biological degradation.Preferred UV light absorber is compounds such as the salicylate class that can buy from the market, benzophenone, benzotriazole category among the present invention, and its consumption is 0.001-0.8 part (weight)/100 part polystyrene, preferred 0.1-0.5 part/per 100 polystyrene.
Embodiment one is to example eight
The major equipment of preparation expandable bead is a reactor, and agitator is housed in the still, uses steam heating, and operating pressure is 1.0 MPas.Reactor is equipped with reinforced and blow-dry device.
Wherein embodiment one to embodiment three is the prescription of preparation coventional type EPS, and embodiment four to embodiment eight is the prescription of preparation flame retardant type EPS.Embodiment one to embodiment eight is for two-step approach prepares controllable biologically degraded polystyrene, and promptly after preparing expandable bead, [embodiment 1 and 4 uses Fe to place photosensitizers again
3O
4-propyl group nickel, embodiment 2,3,5,6,7 and 8 uses Fe
3O
4-two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) nickel], to put into the pre-frothing machine and carry out pre-frothing, its operating process is as follows:
Embodiment one:
1,100 parts of polystyrene beads after reinforced will the screening add in the reactor through pipeline with gas blower, add 8 parts of sherwood oils then successively, 160 parts of water, 2 parts of Sodium dodecylbenzene sulfonatees.
2, dipping absorbs reinforced finishing, and feeds steam heating (feeding part nitrogen before the heating earlier) in reacting kettle jacketing, whipping agent gasification at this moment, the still internal pressure increases, and is controlled at about 1.0 MPas, and the material temperature remains on 80 ℃, be incubated 4-12 hour, be cooled to then below 40 ℃ and get final product discharging.Bead is deposited under lesser temps (10-20 ℃), drainage after tap water cleans, and dries up through blow-dry device then, and pack was sealed up for safekeeping about 15 days, can use.
3, the expandable bead after pre-frothing is stored adds 4 parts of photosensitizerss (wherein iron-nickel compound weight ratio is 1: 0.3), and makes photosensitizers equably on the surface attached to the EPS bead, and temperature is carried out the expanded foamed pearl foam beads that makes more than 90 ℃.Foam beads after the pre-frothing requires its loose density to reach the density of moulded products regulation.Type of heating adopts water vapor pre-frothing.
4, slaking maturation process is carried out in cloth bag or large-scale netted feed bin.Optimum curing temperature is 22-26 ℃; Curing time is different because of pre-frothing particulate loose density, shape and ambient environmental conditions.Generally just put into die for molding after at room temperature slaking 8-24 hour.
5, the steam heating moulding is adopted in moulding, and the molding device of use has digester (-tor) and PS foam slab machine.
1. digester (-tor): the pre-frothing particle that slaking is good is filled porous mold, places digester (-tor) then, feeds the steam heating moulding.General vapor pressure is controlled at the 0.05-0.25 MPa, and be 2-3min heat-up time.Pre-frothing particle in the mould is subjected to thermal softening, expansion, and clinkering together mutually.Open digester (-tor) then and take out mould, cooling and demolding obtains controllable biologically degraded polystyrene foam resin.
2.PS foam slab machine
Feeding pressure earlier during moulding is the heating steam of 0.1-0.2 MPa, will open the air outlet behind the mould and die preheating 30s, and with in the pre-frothing particle feeding mould, feeding gauge pressure is the steam of 0.1-0.2 MPa with the pneumatic transmission method.Be 10-30s for the 1-2min(packing articles heat-up time), at this moment temperature of charge is about 110 ℃ in the mould, and particle is softening, and the expansion clinkering is an one, steam off joint door after insulation for some time, the water flowing cooling and demolding promptly obtains controllable biologically degraded foam plastic product.Decide on the thickness of product size size and wall cooling time.
Embodiment four:
1, reinforced with in 100 parts of polystyrene beads adding reactors of gas blower after pipeline will screen, add 8 parts of sherwood oils then successively, 190 parts of water, 2.5 part Sodium dodecylbenzene sulfonate, 3 parts of tetrabromoethanes, 0.4 part of dicumyl peroxide, 0.3 part 2, the 6-ditertbutylparacresol, 0.2 part of benzophenone.
2, dipping absorbs 4-14hr, and operating process and condition are with embodiment one.
3, in expandable bead, add 3 parts of iron-nickel photosensitizerss (wherein iron-nickel compound weight ratio is 1: 0.4) powder, carry out pre-frothing, operating process and condition are with embodiment one.
4, put into die for molding behind the slaking 8-24hr, operating process and condition are with embodiment one.
5, adopt digester (-tor) or PS foam forming machine to carry out the steam heating moulding, cooling and demolding obtains the controllable biologically degraded type polystyrene resin of flame retardant type, and operating process and condition are with embodiment one.
Embodiment nine to 25
Embodiment nine to 25 prepares controllable biologically degraded polystyrene (referring to table two) for single stage method, promptly adds photosensitizers Fe in reactor
2O
3-organic nickel (embodiment nine to 22) or ZrO
2-organic nickel (embodiment 23 to 24), or CeO
2-organic nickel (embodiment 25), photosensitizers infiltrates through in the polystyrene bead under the heating and pressurizing condition, retains in after the cooling in the bead, directly makes the controllable biologically degraded polystyrene bead of expandability.Wherein embodiment nine to 13 is the prescription of preparation coventional type degraded EPS, and embodiment 14 to 25 is the prescription (table two) of preparation flame retardant type degraded EPS, and its operating process is as follows:
Embodiment nine:
1,100 parts of polystyrene beads after reinforced will the screening, add in the reactor through pipeline with gas blower, add 8 parts of sherwood oils then successively, 200 parts of water, 6 parts of photosensitizerss (wherein ferric oxide and nickel compound weight ratio are 1: 0.6), 3 parts of Sodium dodecylbenzene sulfonatees.
2, dipping absorbs 8-24hr, auxiliary agents such as whipping agent, photosensitizers is infiltrated through in the polystyrene bead under the heating and pressurizing condition, and make its swelling, and its operating process and other condition are with embodiment one.
3, put into die for molding behind the slaking 8-24hr, operating process and condition are with embodiment one.
4, expandable bead is put into the pre-frothing machine and carried out pre-frothing.Operating process and condition are with embodiment one.
5, adopt digester (-tor) or PS foam forming machine to carry out the steam heating moulding, cooling and demolding obtains controllable biologically degraded type polystyrene resin, and operating process and condition are with embodiment one.
Embodiment 14:
1,100 parts of polystyrene beads after reinforced will the screening, add in the reactor through pipeline with gas blower, add 9 parts of sherwood oils then successively, 200 parts of water, 3 parts of photosensitizerss (wherein ferric oxide and nickel compound weight ratio are 1: 0.4), 3 parts of Sodium dodecylbenzene sulfonatees, 3 parts of tetrabromoethanes, 0.4 part dicumyl peroxide, 0.2 part of 1-hydroxy-3-methyl-4-isopropyl benzene, 0.4 part of benzophenone.
2, dipping absorbs 8-24hr, and its operating process and condition are with embodiment nine.
3, put into die for molding behind the slaking 8-24hr, operating process and condition are to embodiment one.
4, expandable bead that slaking is good is put into the pre-frothing machine and is carried out pre-frothing, and operating process and condition are with embodiment one.
5, adopt digester (-tor) or PS foam forming machine to carry out the steam heating moulding, cooling and demolding obtains the controllable biologically degraded type polystyrene resin of flame retardant type, and operating process and condition are with embodiment one.
Annotate: embodiment nine and 14 uses Fe
2O
3-decyl nickel photosensitizers,
Embodiment ten and 15 uses Fe
2O
3With 2,2 '-mixture of thiobis (uncle's 4-octyl phenol oxygen base) nickel-n-Butyl Amine 99 complex compound is as photosensitizers,
Embodiment 11 and 16,17,18 uses Fe
2O
3With 2,2 '-mixture of thiobis (uncle's 4-octyl phenol oxygen base) nickel-2 ethyl hexylamine complex compound is as photosensitizers,
Embodiment 12,13 and 19 to 22 uses Fe
2O
3With the mixture of dioctyl dithiocarbamic acid nickel as photosensitizers,
The photosensitizers of embodiment 23 to 24 is ZrO
2-decyl nickel,
The photosensitizers of embodiment 25 is CeO
2-dibenzyl aminodithioformic acid nickel.
Embodiment one to embodiment 25, according to the amount of allocating into of adjusting photosensitizers and the different proportionings of contained two components thereof, and adjusts the add-on of various auxiliary agents simultaneously, can make the controllable biologically degraded polystyrene foam resin of different inductive phases.
Also can be added with treated starch in the polystyrene foam resin of the present invention, its content is 5-40 part treated starch/per 100 parts of polystyrene resins.Wherein treated starch is the treated starch that white existing technology is made, and this technology is for example at EP327,505, JP4,202,565(92) and US5, disclosure is arranged in 059,642.
Claims (9)
1, a kind of controllable biologically degraded polystyrene foam resin, it contains:
1) 100 parts of polystyrene,
2) 6-12 part whipping agent,
3) 140-240 part dispersion medium,
4) 1-8 part tensio-active agent,
5) 1-12 part is as the mixture of iron cpd, Zirconium oxide, cerium oxide and the organic nickel compound of photosensitizers with optionally use 0.001-0.8 part UV light absorber, and wherein umber by weight.
2, according to the controllable biologically degraded polystyrene foam resin of claim 1, wherein, polystyrene is the expandable bead polystyrene by the suspension method preparation; Photosensitizers is the mixture of ferriferous oxide, Zirconium oxide or cerium oxide and organic nickel; Whipping agent is lower boiling fat hydrocarbon or halogenated aliphatic hydrocarbon class.
3, according to the controllable biologically degraded polystyrene foam resin of patent requirement 2, wherein photosensitizers is Fe
2O
3, Fe
3O
4, ZrO
2Or CeO
2With C
1-80Alkyl nickel, C
1-80Alkoxyl group nickel, C
1-80Alkylthio nickel, two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids list second fat) nickel, 2,2 '-thiobis (uncle's 4-octyl phenol oxygen base) nickel-n-Butyl Amine 99 complex compound, 2,2 '-thiobis (uncle's 4-octyl phenol oxygen base) nickel-2 ethyl hexylamine complex compound, 2,2 '-thiobis (uncle's 4-octyl phenol oxygen base) nickel and N, N-two C
1-80The mixture of alkyl dithiocarbamic acid nickel and analogue thereof; Whipping agent is sherwood oil, propane, butane, pentane or their mixture and isomer thereof.
4, according to the controllable biologically degraded polystyrene foam resin of claim 3, wherein organic nickel is two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids list second fat) nickel, 2,2 '-thiobis (uncle's 4-octyl phenol oxygen base) nickel-n-Butyl Amine 99 complex compound, 2,2 '-thiobis (uncle's 4-octyl phenol oxygen base) nickel-2 ethyl hexylamine complex compound, 2,2 '-thiobis (uncle's 4-octyl phenol oxygen base) nickel, and N, N-two C
1-30Alkyl dithiocarbamic acid nickel and analogue thereof.
5, according to claim 1,2,3 or 4 controllable biologically degraded polystyrene foam resin, it can include 0.001～0.8 part of UV light absorber, 0.2～0.6 part of organic compound oxidation inhibitor, 0.2～0.9 part of organo-peroxide linking agent, 2～5 parts of fire retardants, wherein umber all by weight.
6, according to the controllable biologically degraded polystyrene foam resin of claim 5, wherein UV light absorber is benzophenone, salicylate class and benzotriazole compound; Oxidation inhibitor is 1-hydroxy-3-methyl-4-isopropyl benzene, 2,6 di t butyl phenol, 2,6 ditertiary butyl p cresol; Linking agent is dicumyl peroxide, benzoyl peroxide;
Fire retardant is tetrachloroethane, tetrabromoethane, weisspiessglanz, pentabromo-ethylbenzene, pentabromochlorocyclohexane, tribromo phenyl allyl ether, tetrabromo-bisphenol allyl ethers etc.
7,, wherein also contain 10-40 part treated starch/per 100 parts of polystyrene according to the polystyrene foam resin of claim 1.
8, a kind of method for preparing controllable biologically degraded polystyrene foam resin may further comprise the steps:
(1) reinforced: the polystyrene bead in reactor after 100 parts of (weight) screenings of adding, 6-12 part (weight) whipping agent, 140-240 part (weight) dispersion medium, 1-8 part (weight) tensio-active agent, optionally use 2-5 part (weight) fire retardant, 0.2-0.9 part (weight) linking agent, 0.2-0.6 part (weight) organic antioxidant, 0.001-0.8 part (weight) UV light absorber;
(2) dipping absorbs: reinforced finishing, in reacting kettle jacketing, feed steam heating (feeding part nitrogen before the heating earlier), and the still internal pressure is controlled at below 1.0 MPas, expect warm 80-100 ℃, insulation 4-12hr is cooled to then below 40 ℃ and gets final product discharging, and this material is expandable polystyrene bead;
(3) in expandable bead, (both weight ratios are 1: 0.1 to 1: 0.95 as ferriferous oxide, Zirconium oxide or the cerium oxide of photosensitizers and the mixture of organic nickel to add 1-12 part (weight), and make photosensitizers equably on the surface attached to expandable polystyrene bead, carry out the expanded foamed pearl foam beads that makes through temperature more than 90 ℃;
(4) put into die for molding behind the slaking 8-24hr.
9, a kind of method for preparing the controllable biologically degraded polystyrene bead of expandability, this method comprises:
(1) reinforced: the polystyrene bead in reactor after 100 parts of (weight) screenings of adding, 6-12 part (weight) whipping agent, 140-240 part (weight) dispersion medium, 1-12 part (weight) is as the photosensitizers ferriferous oxide, the mixture of Zirconium oxide or cerium oxide and organic nickel (both weight ratios are 1: 0.1 to 1: 0.95), 1-8 part (weight) tensio-active agent, optionally use 2-5 part (weight) fire retardant, 0.2-0.9 part (weight) linking agent, 0.2-0.6 part (weight) organic antioxidant, 0.001-0.8 part (weight) UV light absorber;
(2) dipping absorbs: reinforced finishing, in reacting kettle jacketing, feed steam heating (feeding part nitrogen before the heating earlier), the still internal pressure is controlled at below 1.0 MPas, expect warm 80-100 ℃, insulation 8-24hr, lowering the temperature then gets final product discharging below 40 ℃, and this material is the controllable biologically degraded polystyrene bead of expandability.
(3) expandable polystyrene bead carries out the expanded foamed pearl foam beads that makes through temperature more than 90 ℃;
(4) put into die for molding behind the slaking 8-24hr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94105049A CN1034737C (en) | 1994-05-13 | 1994-05-13 | Controllable light biodegradation polystyrene foam resin and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94105049A CN1034737C (en) | 1994-05-13 | 1994-05-13 | Controllable light biodegradation polystyrene foam resin and its preparing method |
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| CN1097773A true CN1097773A (en) | 1995-01-25 |
| CN1034737C CN1034737C (en) | 1997-04-30 |
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ID=5031858
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344704C (en) * | 2002-08-07 | 2007-10-24 | 大科能树脂有限公司 | Low heat storing thermoplastic resin composition and molding thereof |
| CN103788521A (en) * | 2014-01-22 | 2014-05-14 | 南通市海鸥救生防护用品有限公司 | Antiflaming and uvioresistant polystyrene foam material and preparation method thereof |
| CN105856468A (en) * | 2016-06-08 | 2016-08-17 | 惠州景华包装制品有限公司 | EPS temperature-increasing pressurizing curing process |
| CN108864468A (en) * | 2018-05-30 | 2018-11-23 | 天津斯坦利新型材料有限公司 | Expandable polystyrene material and its preparation method and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4360606A (en) * | 1972-10-26 | 1982-11-23 | Owens-Illinois, Inc. | Photo-degradable polymer compositions |
| JPS6041344A (en) * | 1983-08-15 | 1985-03-05 | Fuji Facom Corp | Managing system of generation time of generated data |
| KR910700301A (en) * | 1988-12-22 | 1991-03-14 | 리챠드 지. 워터맨 | Photodegradants and Heat-Adhesives for Polymeric Matrix Materials |
-
1994
- 1994-05-13 CN CN94105049A patent/CN1034737C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344704C (en) * | 2002-08-07 | 2007-10-24 | 大科能树脂有限公司 | Low heat storing thermoplastic resin composition and molding thereof |
| CN103788521A (en) * | 2014-01-22 | 2014-05-14 | 南通市海鸥救生防护用品有限公司 | Antiflaming and uvioresistant polystyrene foam material and preparation method thereof |
| CN105856468A (en) * | 2016-06-08 | 2016-08-17 | 惠州景华包装制品有限公司 | EPS temperature-increasing pressurizing curing process |
| CN108864468A (en) * | 2018-05-30 | 2018-11-23 | 天津斯坦利新型材料有限公司 | Expandable polystyrene material and its preparation method and application |
| CN108864468B (en) * | 2018-05-30 | 2021-10-26 | 天津斯坦利新型材料有限公司 | Expandable polystyrene material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1034737C (en) | 1997-04-30 |
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