CN1800249A - Biodegradable starch-base foaming composition and foaming product containing same - Google Patents
Biodegradable starch-base foaming composition and foaming product containing same Download PDFInfo
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- CN1800249A CN1800249A CN 200510000030 CN200510000030A CN1800249A CN 1800249 A CN1800249 A CN 1800249A CN 200510000030 CN200510000030 CN 200510000030 CN 200510000030 A CN200510000030 A CN 200510000030A CN 1800249 A CN1800249 A CN 1800249A
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Abstract
The invention relates to a component of starch group form product with biological degradability and it's preparing method. The density of the form product is 0.5-0.002g/cm2 with different sharps. The materials of the form product at least comprise: 40-95 parts of thermoplastic starch, 0.2-40 parts of rubber polymer, 0.5-35 parts of thermoplastic resin polymer, 10-50 parts of plasticity agent, 1-40 parts of foaming agent, 0.1-5 parts of forming nucleary agent, 0.01-2 parts of molecular weight converter and 0.1-6 parts of thermoplastic elastopolymer film. The form product is formed by sequencing the single interlock or double interlocks; it uses rotation spraying method to coat the thermoplastic elastomeric polymer to obtain the starch group form product at 30-200 deg.
Description
Technical field
The present invention designs biodegradable starch base foaming product and preparation method thereof.
Background technology
Along with Chinese economic development, the consumption of wrapping material is huge day by day, wrapping material are that the basis makes with the oil with the starting material of foaming products such as polystyrene, polyvinyl chloride, urethane mostly at present, have nondegradable performance, become global public hazards just day by day.And but the starch base foaming product has the biological nature of natural degradation, is particularly suitable environmental friendliness wrapping material.The foaming product investigator is carrying out unremitting effort in this field always both at home and abroad, and the inventor of CN1381519A is aided with some auxiliary agents with rosin and starch and is foamed into the foam material with certain intensity.The inventor of JP106233/2001 by make methods such as the starch molecule ball condenses on vegetable fibre, is mixed and made into foam material with itself and Plastic Resin with vegetable fibres such as starch, shredded paper, timber.WO9/02023 investigator is a raw material with ethene, vinyl alcohol, ethylene-acrylic acid copolymer, is that whipping agent is prepared foaming product or the like with the polymeric acid.Preparation method about degradable foamed goods has some kinds, but in these disclosed researchs, foam article exists product size instability, product size to change the problem that waits greatly with temperature humidity.
Summary of the invention
The purpose of this invention is to provide biodegradable starch base foaming product, by technical finesse of the present invention, the size of its goods, elasticity, physical strength have certain stability.
Its density of starch-based bio degradable foaming wrapping material that the present invention makes is 0.5-0.002g/cm
2, described foam has unicellular structure, and they can be different shapeies, and the formation material of these foams comprises:
The thermoplastic starch of 40-95 part (weight part)
0.2-40 the rubber polymer (weight part) of part
0.5-35 the thermoplastic resin polymer (weight part) of part
The softening agent of 10-50 part (weight part)
The whipping agent of 1-40 part (weight part)
0.1-5 the surface-modifying agent (weight part) of part
0.05-5 the foaming nucleation agent (weight part) of part
0.01-2 the molecular weight properties-correcting agent (weight part) of part
0.1-6 part thermoplastic elastomeric polymer (weight part)
Constitute and exist one or more can improve the thermoplastic polymer of mixture melt strength in the mixing element of above-mentioned foam beads, exist one or more can improve the properties-correcting agent of mixture molecular weight (or network structure), one or more make foams have elastic rubber polymer, make foams have one or more elastomeric polymer films of dimensional stability.
The used starch of the present invention generally is the mixture of amylose starch and amylopectin, and the diameter range of starch is generally 1-50 μ m.Preferred high straight chain (referring to that straight chain content surpasses 25%) starch can be W-Gum, yam starch and other cereal starchs.Starch of the present invention can also be to use the starch of physics or chemical process modification, as treated starches such as ethylene-acrylic acid graft starch, EMA acid anhydride graft starch, ethylene-propylene acetoacetic ester-maleic anhydride terpolymer graft starch, propionic ester starch, ethoxylated starches, oxypropylated starches, acetic ester treated starch, propionic ester starch, butyric ester treated starches.
Its limiting viscosity of the starch that the present invention uses (recording as solvent with dimethyl sulfoxide (DMSO)) is between 1.5-0.03dl/g.
No matter the starch that the present invention uses is that native starch or treated starch all need not carry out any processed when the preparation foaming product.
Be used to make the rubber polymer of this starch base foaming product, be meant the polymkeric substance that can form title complex with the starch interaction or be cross-linked to form blend, generally be some natural or synthetic rubber-like latex or low-molecular(weight)polymer rubber, for example, natural rubber latex, polychloroprene latex, polyacrylic ester latex, poly-alkyl epoxy base latex, PBAA ester gum breast, waterborne polyester based polyurethane latex, water-based polyethers based polyurethane latex, polyvinylchloride latex, thiokol latex etc.Be used for the mixture that natural rubber polymkeric substance of the present invention also comprises above-mentioned two kinds or some kinds of latex.The rubber polymer that is used to make the starch base foaming product comprises that also above-mentioned one or more uncrosslinked blended hang down molecule rubber, and its molecular weight is generally the 500-50000 scope.
The rubber polymer that is used to make the starch base foaming product generally be soluble or add certain surface-modifying agent after can be prepared into emulsion.This surface-modifying agent generally is one or more in anion surfactant, cats product, the nonionogenic tenside or the like, as sodium laurylsulfonate (SDS), Tween-60, span-80, OP-10 or the like.The water molecules that can contain any weight part in rubber that the present invention is used or the latex.The content of water can be regulated with flash distillation or vacuum distillation method or other method.
Any type of interaction can take place with starch in one or more rubber polymers or the mixture that are used to make the starch base foaming product.
The thermoplastic polymer that is used to prepare the starch base foam material be generally some can with above-mentioned starch or the good hydrophilic natural or synthetic polymer of rubber polymer consistency.These polymkeric substance generally comprise chitosan base polymer, cellulosic polymer such as alkylcellulose class, as methylcellulose gum, butyl cellulose or the like.
The thermoplastic polymer that is used to prepare foam of the present invention can be water miscible natural or synthetic polymer, these polymkeric substance comprise polyvinyl alcohol, polyvinylpyrrolidone class, the polyacrylamide base polymer of various degree of hydrolysis, or the polymkeric substance that obtains through modifications such as borate, phosphoric acid salt of above-mentioned polymkeric substance.Or the ampholyte copolymer that adopts water base modification hydrophobic polymer of some close relatives to obtain.These polymkeric substance comprise ethylene-vinyl alcohol-based copolymer, ethylene-acrylate copolymer.
Crosslinked or other any type of interactions can take place at its plasticizing process and starch or rubber polymer in the thermoplastic polymer that is used for making the starch base foaming product.
Starch base foaming product of the present invention also comprises one or more softening agent, comprises water, glycerine, sorbyl alcohol, low-molecular-weight polyethylene glycol, dimethyl formamide, N.F,USP MANNITOL, urea, dimethyl sulfoxide (DMSO) etc.This softening agent comprises above-mentioned a kind of or wherein multiple binding substances.
Starch base foaming product of the present invention also comprises one or more whipping agents.Described whipping agent can be pneumatogen or chemical foaming agent.Pneumatogen such as water, low mass molecule alcohol, ether, halohydrocarbon or the like; Chemical foaming agent generally is an azo class chemical foaming agent, as Cellmic C 121 (AC whipping agent), and barium azo-biscarbonate, azo two carbonic acid diisopropyl esters; Nitroso group foaming agent, as N, N '-dinitrobenzene five methyne tetramines, N, N '-dimethyl-N, N '-dinitrosoterephthalamine; Benzol sulfohydrazide class whipping agent is as benzol sulfohydrazide, 4,4 '-OBSH etc.; Carbonate whipping agent such as volatile salt, bicarbonate of ammonia etc.Used whipping agent comprises above-mentioned a kind of or wherein multiple binding substances.
Except that whipping agent, also comprise some frothing aids in the foaming product of the present invention, as zinc oxide, lead carbonate, borax, thanomin, stearyl chloride, fatty amine, maleic anhydride, phthalate anhydride etc.
Also contain nucleator in the starch base foam article of the present invention.The consumption of nucleator is 0.005-5 part (weight part), used nucleator is mineral compound such as lime carbonate, talcum powder, white carbon black etc., can also add titanic acid ester when nucleator adds, silane waits the consistency of improving with starch, rubber and nucleator.In addition, can also fill some organic class powder, as wood powder, cellulose powder or the like, described nucleator can join in the mixture of making foams, or makes master batch and add when extrusion foaming.
Also contain the elastomeric polymer film in the starch base foam article of the present invention, be meant that some have the thermoplastic emulsion's type tackiness agent or the hot melt adhesive of different hydrophilic and hydrophobic energy.These tackiness agents comprise polyvinyl alcohol adhesive, polyurethane kind tackiness agent, polyisobutene class tackiness agent, chloroprene rubber class tackiness agent, chlorosulfonated polyethylene resin class tackiness agent or the like.These tackiness agents can also be the polymer alloy tackiness agent, comprise phenolic aldehyde-polyvinyl butyral acetal alloy glue, phenolic aldehyde-chloroprene rubber alloy glue, phenolic aldehyde-organosilicon alloy glue, epoxy polyurethane alloy glue, epoxy-polyvinylacetal alloy glue etc.Can also be some natural gelatin or vegetable jelly etc.This type of tackiness agent is forming elementary foam or the goods formation initial stage, foaming product has just gone out extruding dies, or just from forming mould during the demoulding, in foam has 30-200 ℃ of temperature range, attached to the foam outside surface, the thickness of described thermoplasticity elastomer film is between 5-80um with above-mentioned one or more glue for the mode of use rotary spray or spraying.Described thermoplastic elastomeric polymer film may stop the 5-150s time under 30-200 ℃ of hot gas flow after being attached to the foam surface, cool off in normal temperature or freezing air.
The molecular weight properties-correcting agent that also can contain 0.01-2 part in the starch base foam article of the present invention, as formaldehyde, butyraldehyde, dibenzoyl peroxide, persulphate etc., perhaps their binding substances.Strengthening agent such as glass fibre, talcum powder etc.Different application be can also have more and suitable insect-proof agent, mould inhibitor, fire retardant etc. added.Also may use a small amount of releasing agent etc. during the demoulding again.All kind and consumption use above-mentioned auxiliary agent routinely.
Preparation starch base foaming product of the present invention is with the mixture based on starch, joins in single screw rod of any length-to-diameter ratio or the twin screw extrusion foaming or foams with compression molding.Equipment need promptly not can be used for producing foaming product through special transformation, less investment, and technology is easy.
Preparing starch base foaming product method for compositions of the present invention comprises: the rubber polymer (weight part) that adds 0.2-40 part in homogenizer, 0.1-5 part surface-modifying agent (weight part) under 15-80 ℃ temperature high-speed stirring 5-65 minute, then under said temperature to the thermoplastic resin polymer that wherein adds 0.5-35 part (weight part), the softening agent of 10-50 part (weight part), the thermoplastic starch of 40-95 part (weight part), 0.05-5 the foaming nucleation agent (weight part) of part, 0.01-2 stirring after 10-60 minute, the whipping agent (weight part) of molecular weight properties-correcting agent (weight part) 1-40 part of part shakes stock.Above-mentioned stock is added extrusion foaming in single screw rod or the twin screw extruder, and the method for foam shaping by extrusion or moulded from foam moulding all can be used for the moulding of the bright foaming product of this law.The shape of foaming can be granule type or other different shapes.Foaming product is sprayed 0.1-6 part thermoplastic elastomeric polymer (weight part) after going out mould under 30-200 ℃ of following rotary spraying device.
Compare with existing disclosed foaming product, the starch base foaming product that the present invention makes is white in color or oyster white.Have certain mechanical strength, and have higher resilience, satisfy requirements such as shockproof, sound insulation, insulation, can be degraded fully by microorganism after discarded.
Below with example explanation the present invention, but these examples only are used for illustrative purposes, do not constitute any limitation of the invention.(except that rebound resilience, following percentage composition is weight percentage)
Embodiment 1
The composition of the following composition of preparation in homogenizer: the yam starch of 60 parts (weight part, below all with), 15 parts of solid contents are 30 parts polychloroprene latex, 1 part the OP-10 aqueous solution; 5 parts concentration is that the weight-average molecular weight of 10 parts of polyvinylpyrrolidone aqueous solution, polyvinylpyrrolidone is 49000,20 parts sorbyl alcohol, 0.02 the benzoyl peroxide of part, 0.5 part talcum powder are after mixing under 50 ℃, send into ZSK-30 type twin screw extruder, screw speed 138rpm extrudes under 130-150 ℃, the elementary foam of the oyster white that obtains.This foam in the time of 30-200 ℃ by the ball nozzle rotary spray on 0.5 part chloroprene rubber adhesive agent, obtaining diameter after the dry cooling is that 3.5mm, density are 0.10g/cm
3, rebound resilience is 78% oyster white foam.
Embodiment 2
With the mode of embodiment 1, difference is 50% natural rubber latex for the polychloroprene latex among the embodiment 1 being changed to 15 parts with content, and 20 parts sorbyl alcohol is changed to 25 parts glycerol, and other components and fabrication process condition are constant.Can make density is 0.14g/cm
3, rebound resilience 80% foaming product.
Embodiment 3
Mode with embodiment 1, difference is for changing 60 parts yam starch among the embodiment 1 into 80 parts W-Gum, the amount of polychloroprene latex is reduced to 10 parts, 5 parts concentration is that to become 10 parts concentration be 10% the polyvinylpyrrolidone aqueous solution to the 10% polyvinylpyrrolidone aqueous solution, 20 parts sorbyl alcohol becomes 20 parts glycerol, and other components and fabrication process condition are constant.Can make density is 0.23g/cm
3, rebound resilience 68% foaming product.
Embodiment 4
Mode with embodiment 1, difference is 50% natural rubber latex for the polychloroprene latex among the embodiment 1 being changed to 15 parts solid content, 5 parts concentration is that to change 10 parts concentration into be that 2% alcoholysis degree is that 99% polymerization degree is 1700 polyvinyl alcohol water solution for 10% the polyvinylpyrrolidone aqueous solution, 20 parts sorbyl alcohol becomes 25 parts glycerol, obtain behind the elementary foam changing 0.5 part chloroprene rubber adhesive agent into 1 part polyethers based polyurethane glue its spray is coated, can make density 0.08g/cm
3, the foaming product of rebound resilience 85%.
Embodiment 5
Mode with embodiment 1, difference is for to become three-component grafted modification treated starch with the starch among the embodiment 1, polychloroprene latex changes into as water-based polyethers based polyurethane latex, consumption is all constant, 0.02 the benzoyl peroxide of part makes trolamine into, 20 parts sorbyl alcohol becomes 25 parts glycerol, obtains behind the elementary foam changing 0.5 part chloroprene rubber adhesive agent into 1 part polyethers based polyurethane glue its spray is coated, and can make density 0.10g/cm
3, the faint yellow foaming product of rebound resilience 82%.
Embodiment 6
Mode with embodiment 1, difference is for to change the polychloroprene latex among the embodiment 5 into water-based polyethers based polyurethane latex, 0.02 the benzoyl peroxide of part makes trolamine into, 20 parts sorbyl alcohol changes 25 parts glycerol into, obtain the stock that foams after in homogenizer, mixing, this stock is joined in the hot-forming grinding tool, pressurize 600s can obtain elementary foam under the pressure hot pressing of 165 ℃ of 2Mpa, after obtaining elementary foam, with 1 part polyethers based polyurethane glue its spray is coated, can make density 0.25g/cm
3, the faint yellow foaming product of rebound resilience 60%.
Claims (13)
1, a kind of starch-based, biodegradable foaming composition is characterized in that said composition comprises following composition: the surface-modifying agent (weight part) of the softening agent (weight part) of the rubber polymer (weight part) of the thermoplastic starch of 40-95 part (weight part), 0.2-40 part, the thermoplastic resin polymer (weight part) of 0.5-35 part, 10-50 part, the whipping agent (weight part) of 1-40 part, 0.1-5 part, the foaming nucleation agent (weight part) of 0.05-5 part, the molecular weight properties-correcting agent (weight part) of 0.01-2 part, 0.1-6 part thermoplastic elastomeric polymer.(weight part).
2, according to the composition of claim 1, it is characterized in that described rubber polymer is the polymkeric substance that can form title complex with the starch interaction or be cross-linked to form blend, be selected from polychloroprene latex, natural rubber latex, polyacrylic ester latex, poly-alkyl epoxy base latex, poly-butadiene acrylate latex, waterborne polyester based polyurethane latex, water-based polyethers based polyurethane latex, polyvinylchloride latex, thiokol latex.Or the mixture of the low molecule rubber of above-mentioned uncrosslinked one or more blended, latex, its molecular weight is being the 500-50000 scope.
3, the composition of claim 1 is characterized in that described thermoplastic polymer is selected from polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, or the polymkeric substance that obtains through modifications such as borate, phosphoric acid salt of above-mentioned polymkeric substance.
4, arbitrary composition among the claim 1-3, described softening agent is selected from water, glycerine, sorbyl alcohol, low-molecular-weight polyethylene glycol, dimethyl formamide, N.F,USP MANNITOL, urea, dimethyl sulfoxide (DMSO).Perhaps above-mentioned a kind of or wherein multiple binding substances.
5, the foaming product of claim 1-4, it constitutes the molecular weight properties-correcting agent (weight part) that comprises 0.01-2% in the material of foam beads, described molecular weight modification and be selected from formaldehyde, butyraldehyde, dibenzoyl peroxide, persulphate or their binding substances.
6, arbitrary composition among the claim 1-5, wherein said whipping agent is selected from pneumatogens such as water, low mass molecule alcohol, ether, halohydrocarbon; Chemical foaming agent is selected from the azo foaming agent of Cellmic C 121, barium azo-biscarbonate, azo two carbonic acid diisopropyl esters; Be selected from N, N '-dinitrobenzene five methyne tetramines, N, N '-dimethyl-N, N '-dinitrosoterephthalamine, benzol sulfohydrazide, 4, the nitroso group foaming agent of 4 '-OBSH etc.; Be selected from the carbonate whipping agent of volatile salt, bicarbonate of ammonia; And comprise above-mentioned a kind of or wherein multiple binding substances.
7, arbitrary composition among the claim 1-6, wherein said nucleator are the mineral compound that is selected from lime carbonate, talcum powder, white carbon black; And comprise above-mentioned one or more binding substances.
8, each composition among the claim 1-7, wherein said thermoplastic elastomeric polymer is selected from the thermoplastic emulsion's type tackiness agent or the hot melt adhesive of polyvinyl alcohol adhesive, polyurethane kind tackiness agent, polyisobutene class tackiness agent, chloroprene rubber class tackiness agent, chlorosulfonated polyethylene resin class tackiness agent; Be selected from the polymer alloy tackiness agent of phenolic aldehyde-polyvinyl butyral acetal alloy glue, phenolic aldehyde-chloroprene rubber alloy glue, phenolic aldehyde-organosilicon alloy glue, epoxy polyurethane alloy glue, epoxy polyvinylacetal alloy glue.
9, a kind of method for compositions for preparing claim 1, it is characterized in that at first in homogenizer, adding the rubber polymer (weight part) of 0.2-40 part, 0.1-5 part surface-modifying agent (weight part) under 15-80 ℃ temperature high-speed stirring 5-65 minute, then under said temperature to the thermoplastic resin polymer that wherein adds 0.5-35 part (weight part), the softening agent of 10-50 part (weight part), the thermoplastic starch of 40-95 part (weight part), 0.05-5 the foaming nucleation agent (weight part) of part, 0.01-2 stirring after 10-60 minute, the whipping agent (weight part) of molecular weight properties-correcting agent (weight part) 1-40 part of part shakes stock, above-mentioned stock is added extrusion foaming in single screw rod or the twin screw extruder, and foaming product is sprayed 0.1-6 part thermoplastic elastomeric polymer (weight part) after going out mould under 30-200 ℃ of following rotary spraying device.
10, arbitrary composition is used to prepare the purposes of starch-based, biodegradable foaming product among the claim 1-8.
11, a kind of starch-based, biodegradable foaming product that comprises arbitrary composition among the claim 1-8.
12, the preparation method of the foaming product of claim 11, comprise in ratio described in the claim 1 with raw material mix the back evenly after, method moulding with foam shaping by extrusion or moulded from foam moulding, the extrusion temperature of forcing machine is between 130-150 ℃, perhaps according to the size of mould, the foaming stock that obtains after mixing in the homogenizer is joined in the hot-forming grinding tool, hot pressing obtained elementary foam in 600 seconds under the pressure of 130-180 ℃ of following 1-5Mpa., under 30-200 ℃ it was rotated spray emulsion-type or hot-melt adhesive.
13, the preparation method in the claim 12, it is characterized in that just having gone out extruding dies at foaming product, or after just the demoulding has formed elementary foam from forming mould, in foam has 30-200 ℃ of temperature range, the mode of using rotary spray or spraying with tackiness agent attached to the foam outside surface, the thickness of described thermoplasticity elastomer film is between 5-80um, described thermoplastic elastomeric polymer film is after being attached to the foam surface, under 30-200 ℃ of hot gas flow, stop 5-150 time second, in normal temperature or freezing air, cool off.
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| CN 200510000030 CN1800249A (en) | 2005-01-05 | 2005-01-05 | Biodegradable starch-base foaming composition and foaming product containing same |
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| CN 200510000030 CN1800249A (en) | 2005-01-05 | 2005-01-05 | Biodegradable starch-base foaming composition and foaming product containing same |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712409A (en) * | 2009-06-22 | 2012-10-03 | 全球专利技术公司 | Biodegradable packaging of starch and fiber made by extrusion |
| CN103044719A (en) * | 2012-12-19 | 2013-04-17 | 华南理工大学 | Thermoplastic starch plastic with high hydrophobic property and preparation method thereof |
| CN104419014A (en) * | 2013-09-10 | 2015-03-18 | 丁飞鹏 | Environment-friendly rubber and plastic product foaming agent |
| TWI494323B (en) * | 2013-08-30 | 2015-08-01 | Ind Tech Res Inst | Modified starch compositions, starch composite foam materials and method for preparing the starch composite foam material |
| CN105482146A (en) * | 2014-09-19 | 2016-04-13 | 丁飞鹏 | Environmentally-friendly micro foaming agent |
| CN107129647A (en) * | 2017-06-23 | 2017-09-05 | 广西南宁桂尔创环保科技有限公司 | A kind of fire-retardant degradable environmental protection macromolecule foamed material and preparation method thereof |
| CN107603001A (en) * | 2016-07-11 | 2018-01-19 | 鸿明环保科技股份有限公司 | The composite foamed sheet material of low ratio foamed multiplying power life matter and its manufacture method |
| CN108341994A (en) * | 2018-02-12 | 2018-07-31 | 华南理工大学 | A kind of starch based foam material and preparation method thereof |
| CN108948466A (en) * | 2018-07-13 | 2018-12-07 | 湖州市道场乡资产经营有限公司 | A kind of low resilience high resiliency SBR foam sponge |
| CN109233024A (en) * | 2018-07-13 | 2019-01-18 | 湖州市道场乡资产经营有限公司 | A kind of light weight SBR foam sponge |
| CN109503881A (en) * | 2018-10-27 | 2019-03-22 | 汕头市春叶新材料环保有限公司 | Degradable composite foam material of a kind of antibacterial starch base polyurethane/nano CuO and preparation method thereof |
| WO2019217268A1 (en) * | 2018-05-07 | 2019-11-14 | Cruz Foam, Inc. | Biodegradable foams |
| CN110746635A (en) * | 2019-11-20 | 2020-02-04 | 湖南工业大学 | Composite starch foaming micro-bead and preparation method thereof |
| WO2023028496A3 (en) * | 2021-08-24 | 2023-04-13 | Cruz Foam, Inc. | Biodegradable foams and methods of foam production |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102712409A (en) * | 2009-06-22 | 2012-10-03 | 全球专利技术公司 | Biodegradable packaging of starch and fiber made by extrusion |
| CN103044719A (en) * | 2012-12-19 | 2013-04-17 | 华南理工大学 | Thermoplastic starch plastic with high hydrophobic property and preparation method thereof |
| CN103044719B (en) * | 2012-12-19 | 2015-09-16 | 华南理工大学 | A kind of have thermoplastic starch plastic of high hydrophobicity energy and preparation method thereof |
| US9850362B2 (en) | 2013-08-30 | 2017-12-26 | Industrial Technology Research Institute | Modified starch compositions, starch composite foam materials and method for preparing the starch composite foam material |
| TWI494323B (en) * | 2013-08-30 | 2015-08-01 | Ind Tech Res Inst | Modified starch compositions, starch composite foam materials and method for preparing the starch composite foam material |
| CN104419014A (en) * | 2013-09-10 | 2015-03-18 | 丁飞鹏 | Environment-friendly rubber and plastic product foaming agent |
| CN105482146A (en) * | 2014-09-19 | 2016-04-13 | 丁飞鹏 | Environmentally-friendly micro foaming agent |
| CN107603001A (en) * | 2016-07-11 | 2018-01-19 | 鸿明环保科技股份有限公司 | The composite foamed sheet material of low ratio foamed multiplying power life matter and its manufacture method |
| CN107129647A (en) * | 2017-06-23 | 2017-09-05 | 广西南宁桂尔创环保科技有限公司 | A kind of fire-retardant degradable environmental protection macromolecule foamed material and preparation method thereof |
| CN108341994A (en) * | 2018-02-12 | 2018-07-31 | 华南理工大学 | A kind of starch based foam material and preparation method thereof |
| CN108341994B (en) * | 2018-02-12 | 2020-12-22 | 华南理工大学 | Starch-based foaming material and preparation method thereof |
| WO2019217268A1 (en) * | 2018-05-07 | 2019-11-14 | Cruz Foam, Inc. | Biodegradable foams |
| CN112088184A (en) * | 2018-05-07 | 2020-12-15 | 克鲁兹泡沫有限公司 | Biodegradable foams |
| US20210238393A1 (en) * | 2018-05-07 | 2021-08-05 | Cruz Foam, Inc. | Biodegradable foams |
| CN108948466A (en) * | 2018-07-13 | 2018-12-07 | 湖州市道场乡资产经营有限公司 | A kind of low resilience high resiliency SBR foam sponge |
| CN109233024A (en) * | 2018-07-13 | 2019-01-18 | 湖州市道场乡资产经营有限公司 | A kind of light weight SBR foam sponge |
| CN109503881A (en) * | 2018-10-27 | 2019-03-22 | 汕头市春叶新材料环保有限公司 | Degradable composite foam material of a kind of antibacterial starch base polyurethane/nano CuO and preparation method thereof |
| CN110746635A (en) * | 2019-11-20 | 2020-02-04 | 湖南工业大学 | Composite starch foaming micro-bead and preparation method thereof |
| WO2023028496A3 (en) * | 2021-08-24 | 2023-04-13 | Cruz Foam, Inc. | Biodegradable foams and methods of foam production |
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