CN108102276A - A kind of preparation method of high strength starch plastics - Google Patents
A kind of preparation method of high strength starch plastics Download PDFInfo
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- CN108102276A CN108102276A CN201711303405.2A CN201711303405A CN108102276A CN 108102276 A CN108102276 A CN 108102276A CN 201711303405 A CN201711303405 A CN 201711303405A CN 108102276 A CN108102276 A CN 108102276A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/003—Crosslinking of starch
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract
The present invention relates to field of polymer material preparing technology, and in particular to a kind of preparation method of high strength starch plastics.Starch is modified by epoxychloropropane and succinic anhydride, esterification assigns starch hydrophobicity, crosslinking Treatment increases intermolecular contact and improves its density, add in glass fibre and cobweb, glass fibre and cobweb are modified using silane coupling agent KH 560, it improves the surface-active of glass fibre and reduces voids content, glass fibre plays the humidification of skeleton structure type in starch plastics, so as to improve the mechanical strength of starch plastics, silane coupling agent KH 560 contains epoxy group, there is stronger bonding effect to glass fibre, improve the mechanical strength of starch plastics, maleic anhydride is improved thermoplastic starch and polyacrylic compatibility, further improve the mechanical strength of starch plastics, with extensive prospect of the application.
Description
Technical field
The present invention relates to field of polymer material preparing technology, and in particular to a kind of system of high strength starch plastics
Preparation Method.
Background technology
Plastics are the requirement of daily life, and many facilities are brought to our daily lifes, but with plastic products day
Benefit increases, and the pollution of waste plastic is increasingly severe, though improving the pollution of its environment has become global problem.Plant amylum is made
For natural polymer, there is cheap, abundance, and under natural environment the advantages that fully biodegradable.
Therefore, plastic starch is made in starch by some research units and company both at home and abroad, for producing degradative plastics.
Starch is a kind of natural polymers, and great amount of hydroxy group is contained in molecule, therefore between starch polymer mutually
Active force is very strong, and ative starch is caused to be difficult to melt-processed, and is blended with other polymers in processing and other polymers
Compatibility is also poor.But these hydroxyls such as can be esterified, be etherified, being grafted, being crosslinked at the chemical reactions.Utilize these chemical reactions pair
Starch carries out chemical modification, reduces the hydroxyl of starch, changes its original structure, so as to change the corresponding performance of starch, original
Starch becomes thermoplastic starch.Product made by degradable starch sill has stronger mechanical strength, good flexibility, resists
Impact, temperature tolerance, oil resistant, do not soften, indeformable and good plasticity the features such as.Common general plastic can industrially be replaced
Material, and degradable starch sill is degradable, recoverable, and processing cost is low compared with conventional plastic product.
Biodegradable starch plastics are divided into three classes：Starch filled plastics, starch blending plastics and full-starch plastic.
Starch additive amount in starch filled plastics is generally below 30%, and degradation rate is relatively slow so as to will not all degrade, and be easy to cause again
Secondary pollution；After full-starch plastic decomposes, organic fertilizer can be used as agricultural and will not be adversely affected to changing commanders.
However, the natural high molecular substances such as starch or cellulose in itself in structure and performance there are it is certain the defects of, day
Right polymer substance is blended with polyolefins, and the two is not easy homodisperse and dissolves each other, this can directly affect the mechanical property of plastics.
In addition, it changes humidity quite sensitive, hygroscopic, the mechanical property of product is substantially reduced after water suction, thus application range by
Limitation is arrived.
Therefore, developing a kind of starch plastics that can solve above-mentioned performance issue is highly desirable.
The content of the invention
The technical problems to be solved by the invention：For the natural high molecular substances such as current starch or cellulose and polyolefin
Class is blended, and the two is not easy homodisperse and dissolves each other and hygroscopic, the defects of mechanical strength of plastics is caused to reduce, and provides
A kind of preparation method of high strength starch plastics.
In order to solve the above technical problems, the present invention is using technical solution as described below：
A kind of preparation method of high strength starch plastics, it is characterised in that specifically preparation process is：
（1）200~300g polypropylene heat temperature raisings are weighed, obtain melt polypropylene, 20~26g mistakes are added in into melt polypropylene
Diisopropylbenzene (DIPB), 40~60g maleic anhydrides and 10~12mL acetone are aoxidized, continues heat preservation and is mixed, and pour into dual-screw-stem machine
It squeezes out, obtains modified polypropene；
（2）80~100g buckwheat starch and the mixing of 100~200g cornstarch are weighed, mixing starch is obtained, mixing starch is fallen
Enter after being mixed in the beaker with 4~6 times of deionized waters of mixing starch quality, obtain gelatinized corn starch liquid, natural cooling uses salt
Acid adjusts the pH of gelatinized corn starch liquid, obtains starch mixed liquor, then into starch mixed liquor after 10~12g of addition isoamylases enzymolysis,
Filtering removal filter residue, it is starch reaction liquid to obtain filtrate, and it is molten to add in 12~16mL sodium hydroxides into starch reaction liquid successively
Liquid and 24~30mL epoxychloropropane are mixed, and 8~10g succinic anhydrides are added after being stirred to react, and continue insulated and stirred, obtain
To mixed liquor, mixed liquor is put into nutsch filter and is filtered, removal filtrate is changed to get solids, natural air drying, grinding discharging
Property self-control starch；
（3）It weighs 0.2~0.4kg discarded glass to be put into kiln after fusing, obtains glass solution, glass solution is poured into porous
Wire drawing in bushing, cooled to room temperature obtain self-control glass fibre, and self-control glass fibre and cobweb are mixed and are placed in spider
It is impregnated in the silane coupling agent KH-560 of 1~3 times of net quality, natural air drying obtains modified mixture；
（4）It counts in parts by weight, weighs modified polypropene, modified self-control starch, modified mixture, glycerine and atoleine respectively
Sealing and standing is mixed, places into double screw extruder and is kneaded, is granulated, extrusion molding, you can high strength starch base is made
Plastics.
Step（1）The heat temperature raising temperature is 180~240 DEG C, and continuation mixing time is 1~2h.
Step（2）The whipping temp is 75~85 DEG C, and mixing time is 1~2h, and cooling temperature is 35~45 DEG C, salt
The mass fraction of acid adjusts the pH value of gelatinized corn starch liquid as 4~6 for 5%, and hydrolysis temperature is 28~36 DEG C, enzymolysis time for 45~
55min, the mass fraction of sodium hydroxide solution are 4%, and it is 35~45 DEG C that temperature, which is mixed, be mixed the time for 24~
32min, continuation mixing time are 50~60min.
Step（3）The fusion temperature is 1200~1600 DEG C, and fusing time is 12~16min, and wire drawing rotating speed is 100
~200r/min, the mass ratio for making glass fibre and cobweb by oneself is 1：2, soaking time is 1~2h.
Step（4）The meter in parts by weight weighs 30~40 parts of modified polypropenes, 20~30 parts of modified self-controls respectively
Starch, 10~12 parts of modified mixtures, 4~6 parts of glycerine and 3~5 parts of atoleines, time of repose are 2~4h, and melting temperature is
160~240 DEG C, mixing time is 1~3h.
Compared with other methods, advantageous effects are the present invention：
（1）The present invention is dual modified to mixing starch progress by epoxychloropropane and succinic anhydride, in the effect of modified starch
Under, polypropylene and material is made to form the interface of some strength, esterification can be substituted by hydroxyl assigns starch hydrophobicity, at crosslinking
Reason can increase in starch structure and hand over to increase intramolecule and intermolecular contact in the random site of starch granules
The density of connection, so as to limit the absorption of moisture so that the starch with certain viscosity is dispersed in polypropylene surface, and enhancing is formed sediment
Powder and polyolefins compatibility, then chemically reacted by the way that graft copolymerization, oxidation and esterification occurs with the activity hydroxy in starch, promote
Into the content for reducing surface hydroxyl, achieve the purpose that hydrophobic, improve the water proofing property and mechanical strength of starch plastics；
（2）The present invention adds glass fibre and cobweb, and glass fibre and cobweb are total to using silane coupling agent KH-560
With being modified, since silane coupling agent KH-560 changes the surface characteristic of glass fibre, so as to improve the reaction of the surface of glass fibre
Activity and voids content is reduced, make glass fibre and starch, polypropylene matrix strong bonded on interface, glass fibre is forming sediment
The humidification of skeleton structure type is played in powder base plastics, when material stress, stress along glass fibre transfers and it is rapid
Diffusion, prevents the growth of crackle, so as to improve the mechanical strength of starch plastics, wherein silane coupling agent KH-560 contains ring
Oxygroup, it is not only stronger with polypropylene combination, also there is stronger bonding effect to glass fibre, to starch plastics internal holes
Gap is effectively filled, and improves the mechanical strength of starch plastics again；
（3）The present invention is grafted to poly- third with mechanical strength using maleic anhydride under the initiation of cumyl peroxide
It on alkene chain, and reacts to form ester bond and hydrogen bond between polypropylene and maleic anhydride and the hydroxyl group of starch, makes thermoplastic
Property starch and polyacrylic compatibility improved, further improve the mechanical strength of starch plastics, there is extensive use
Prospect.
Specific embodiment
It weighs 200~300g polypropylene and is heated to 180~240 DEG C, melt polypropylene is obtained, into melt polypropylene
Add in 20~26g cumyl peroxides, 40~60g maleic anhydrides and 10~12mL acetone, continue heat preservation be mixed 1~
2h, and pour into dual-screw-stem machine and squeeze out, modified polypropene is obtained, 80~100g buckwheat starch is weighed and 100~200g corns forms sediment
Powder mixes, and obtains mixing starch, mixing starch is poured into the beaker with 4~6 times of deionized waters of mixing starch quality, in temperature
After spending for 1~2h is mixed at 75~85 DEG C, gelatinized corn starch liquid is obtained, naturally cools to 35~45 DEG C, be 5% with mass fraction
Hydrochloric acid adjusts the pH value of gelatinized corn starch liquid to 4~6, obtains starch mixed liquor, then the different starch of 10~12g is added in into starch mixed liquor
After enzyme digests 45~55min at 28~36 DEG C, filtering removal filter residue, it is starch reaction liquid to obtain filtrate, successively to starch
The sodium hydroxide solution and 24~30mL epoxychloropropane that 12~16mL mass fractions are 4% are added in reaction solution, 35~45
24~32min is mixed at DEG C, 8~10g succinic anhydrides are added after being stirred to react, continues 50~60min of insulated and stirred, obtains
To mixed liquor, mixed liquor is put into nutsch filter and is filtered, removal filtrate is changed to get solids, natural air drying, grinding discharging
Property self-control starch, weigh 0.2~0.4kg discarded glass be put into 1200~1600 DEG C of kiln melt 12~16min after, obtain
Glass solution pours into glass solution in porous bushing, the wire drawing in the case where rotating speed is 100~200r/min, cooled to room temperature,
Self-control glass fibre is obtained, is in mass ratio 1：Self-control glass fibre and cobweb mixing are placed in 1~3 times of cobweb quality by 2
Silane coupling agent KH-560 in impregnate 1~2h, natural air drying obtains modified mixture, counts in parts by weight, weigh 30 respectively
~40 parts of modified polypropenes, 20~30 parts of modified self-control starch, 10~12 parts of modified mixtures, 4~6 parts of glycerine and 3~5 parts of liquid
Body paraffin mixes 2~4h of sealing and standing, places into double screw extruder, is kneaded 1~3h in the case where temperature is 160~240 DEG C, makes
Grain, extrusion molding, you can high strength starch plastics are made.
Example 1
It weighs 200g polypropylene and is heated to 180 DEG C, obtain melt polypropylene, 20g peroxidating is added in into melt polypropylene
Diisopropylbenzene (DIPB), 40g maleic anhydrides and 10mL acetone continue heat preservation and 1h are mixed, and pours into dual-screw-stem machine and squeeze out, and are changed
Property polypropylene, weigh 80g buckwheat starch and the mixing of 100g cornstarch, obtain mixing starch, mixing starch is poured into mixed
In the beaker for closing 4 times of deionized waters of starch quality, after 1h is mixed at temperature is 75 DEG C, gelatinized corn starch liquid is obtained, it is naturally cold
But to 35 DEG C, with the pH value that mass fraction is 5% hydrochloric acid adjusting gelatinized corn starch liquid to 4, starch mixed liquor is obtained, then is mixed to starch
After addition 10g isoamylases digest 45min at 28 DEG C in liquid, filtering removal filter residue, it is starch reaction liquid to obtain filtrate, according to
The sodium hydroxide solution and 24mL epoxychloropropane that 12mL mass fractions are 4% are added in the secondary liquid to starch reaction, at 35 DEG C
24min is mixed, 8g succinic anhydrides are added after being stirred to react, continues insulated and stirred 50min, obtains mixed liquor, will mix
Liquid is put into nutsch filter suction filtration, and removal filtrate obtains modified self-control starch, weigh to get solids, natural air drying, grinding discharging
0.2kg discarded glass is put into 1200 DEG C of kiln after fusing 12min, obtains glass solution, glass solution is poured into porous leakage
It is wire drawing under 100r/min in rotating speed, cooled to room temperature obtains self-control glass fibre, is in mass ratio 1 in plate：2 will be certainly
Glass fibre and cobweb mixing processed, which is placed in the silane coupling agent KH-560 of 1 times of cobweb quality, impregnates 1h, and natural air drying obtains
It to modified mixture, counts in parts by weight, weighs 30 parts of modified polypropenes respectively, 20 parts of modified self-control starch, 10 parts of modifications mix
Object, 4 parts of glycerine and 3 parts of atoleine mixing sealing and standing 2h are closed, are placed into double screw extruder, in the case where temperature is 160 DEG C
1h is kneaded, is granulated, extrusion molding, you can high strength starch plastics are made.
Example 2
It weighs 250g polypropylene and is heated to 210 DEG C, obtain melt polypropylene, 23g peroxidating is added in into melt polypropylene
Diisopropylbenzene (DIPB), 50g maleic anhydrides and 11mL acetone continue heat preservation and 1.5h are mixed, and pours into dual-screw-stem machine and squeeze out, and obtain
Modified polypropene weighs 90g buckwheat starch and the mixing of 150g cornstarch, obtains mixing starch, mixing starch is poured into and is carried
In the beaker of 5 times of deionized waters of mixing starch quality, after 1.5h is mixed at temperature is 80 DEG C, gelatinized corn starch liquid is obtained, from
40 DEG C so are cooled to, the pH value for adjusting gelatinized corn starch liquid with mass fraction for 5% hydrochloric acid obtains starch mixed liquor to 5, then to starch
After addition 11g isoamylases digest 50min at 32 DEG C in mixed liquor, filtering removal filter residue, it is starch reaction to obtain filtrate
Liquid adds in sodium hydroxide solution and 27mL epoxychloropropane that 14mL mass fractions are 4%, 40 into starch reaction liquid successively
28min is mixed at DEG C, 9g succinic anhydrides are added after being stirred to react, continues insulated and stirred 55min, obtains mixed liquor, it will
Mixed liquor is put into nutsch filter suction filtration, and removal filtrate obtains modified self-control starch to get solids, natural air drying, grinding discharging,
It weighs 0.3kg discarded glass to be put into 1400 DEG C of kiln after fusing 14min, obtains glass solution, glass solution is poured into more
It is wire drawing under 150r/min in rotating speed, cooled to room temperature obtains self-control glass fibre, is in mass ratio 1 in the bushing of hole：2
Self-control glass fibre and cobweb are mixed to be placed in the silane coupling agent KH-560 of 2 times of cobweb quality and impregnate 1.5h, it is natural
It air-dries, obtains modified mixture, count in parts by weight, weigh 35 parts of modified polypropenes respectively, starch are made in 25 parts of modifications by oneself, 11 parts
Modified mixture, 5 parts of glycerine and 4 parts of atoleine mixing sealing and standing 3h, place into double screw extruder, are in temperature
2h is kneaded at 200 DEG C, is granulated, extrusion molding, you can high strength starch plastics are made.
Example 3
It weighs 300g polypropylene and is heated to 240 DEG C, obtain melt polypropylene, 26g peroxidating is added in into melt polypropylene
Diisopropylbenzene (DIPB), 60g maleic anhydrides and 12mL acetone continue heat preservation and 2h are mixed, and pours into dual-screw-stem machine and squeeze out, and are changed
Property polypropylene, weigh 100g buckwheat starch and the mixing of 200g cornstarch, obtain mixing starch, mixing starch is poured into mixed
In the beaker for closing 6 times of deionized waters of starch quality, after 2h is mixed at temperature is 85 DEG C, gelatinized corn starch liquid is obtained, it is naturally cold
But to 45 DEG C, with the pH value that mass fraction is 5% hydrochloric acid adjusting gelatinized corn starch liquid to 6, starch mixed liquor is obtained, then is mixed to starch
After addition 12g isoamylases digest 55min at 36 DEG C in liquid, filtering removal filter residue, it is starch reaction liquid to obtain filtrate, according to
The sodium hydroxide solution and 30mL epoxychloropropane that 16mL mass fractions are 4% are added in the secondary liquid to starch reaction, at 45 DEG C
32min is mixed, 10g succinic anhydrides are added after being stirred to react, continues insulated and stirred 60min, obtains mixed liquor, will mix
Liquid is put into nutsch filter suction filtration, and removal filtrate obtains modified self-control starch, weigh to get solids, natural air drying, grinding discharging
0.4kg discarded glass is put into 1600 DEG C of kiln after fusing 16min, obtains glass solution, glass solution is poured into porous leakage
It is wire drawing under 200r/min in rotating speed, cooled to room temperature obtains self-control glass fibre, is in mass ratio 1 in plate：2 will be certainly
Glass fibre and cobweb mixing processed, which is placed in the silane coupling agent KH-560 of 3 times of cobweb quality, impregnates 2h, and natural air drying obtains
It to modified mixture, counts in parts by weight, weighs 40 parts of modified polypropenes respectively, 30 parts of modified self-control starch, 12 parts of modifications mix
Object, 6 parts of glycerine and 5 parts of atoleine mixing sealing and standing 4h are closed, are placed into double screw extruder, in the case where temperature is 240 DEG C
3h is kneaded, is granulated, extrusion molding, you can high strength starch plastics are made.
The starch plastics that comparative example is produced with company of Wuhan City are as a comparison case to high mechanics produced by the present invention
Starch plastics in strength starch base plastics and comparative example are detected, and testing result is as shown in table 1：
1st, mechanics performance determining
Tensile strength, elongation at break, elasticity modulus are detected with reference to GB/T1040.1-2006 standards.
Impact strength is detected with reference to GB/T1043.1-2008 standards.
2nd, water resistance measures
By size about 0.125cm3Extrusion particle weigh（Dry mass）, it is put into after impregnating 30min in 20 DEG C of deionized waters and takes out,
It weighs after blotting surface moisture（Wet weight）.
Water absorption rate=（Wet weight-dry mass）/ dry mass × 100%
Table 1
| Test event | Example 1 | Example 2 | Example 3 | Comparative example |
| Tensile strength（MPa） | 38 | 40 | 41 | 28 |
| Elongation at break（%） | 86 | 87 | 89 | 59 |
| Elasticity modulus（MPa） | 1255 | 1264 | 1270 | 1060 |
| Impact strength（KJ/m2） | 43 | 46 | 48 | 25 |
| Water absorption rate（%） | 13.5 | 13.0 | 12.6 | 33.5 |
According to data in table 1, the intensity of high strength starch plastics produced by the present invention is high, good mechanical performance,
Water absorption rate is low, has good water resistance, solves traditional starch based polyalcohol to humidity sensitive, hygroscopic problem has
Wide prospect of the application.
Claims (5)
1. a kind of preparation method of high strength starch plastics, it is characterised in that specifically preparation process is：
（1）200~300g polypropylene heat temperature raisings are weighed, obtain melt polypropylene, 20~26g mistakes are added in into melt polypropylene
Diisopropylbenzene (DIPB), 40~60g maleic anhydrides and 10~12mL acetone are aoxidized, continues heat preservation and is mixed, and pour into dual-screw-stem machine
It squeezes out, obtains modified polypropene；
（2）80~100g buckwheat starch and the mixing of 100~200g cornstarch are weighed, mixing starch is obtained, mixing starch is fallen
Enter after being mixed in the beaker with 4~6 times of deionized waters of mixing starch quality, obtain gelatinized corn starch liquid, natural cooling uses salt
Acid adjusts the pH of gelatinized corn starch liquid, obtains starch mixed liquor, then into starch mixed liquor after 10~12g of addition isoamylases enzymolysis,
Filtering removal filter residue, it is starch reaction liquid to obtain filtrate, and it is molten to add in 12~16mL sodium hydroxides into starch reaction liquid successively
Liquid and 24~30mL epoxychloropropane are mixed, and 8~10g succinic anhydrides are added after being stirred to react, and continue insulated and stirred, obtain
To mixed liquor, mixed liquor is put into nutsch filter and is filtered, removal filtrate is changed to get solids, natural air drying, grinding discharging
Property self-control starch；
（3）It weighs 0.2~0.4kg discarded glass to be put into kiln after fusing, obtains glass solution, glass solution is poured into more
Wire drawing in the bushing of hole, cooled to room temperature obtain self-control glass fibre, and self-control glass fibre and cobweb are mixed and are placed in spider
It is impregnated in the silane coupling agent KH-560 of 1~3 times of spider web quality, natural air drying obtains modified mixture；
（4）It counts in parts by weight, weighs modified polypropene, modified self-control starch, modified mixture, glycerine and liquid stone respectively
Wax mixes sealing and standing, places into double screw extruder and is kneaded, and is granulated, extrusion molding, you can high strength starch is made
Base plastics.
2. a kind of preparation method of high strength starch plastics according to claim 1, it is characterised in that：Step
（1）The heat temperature raising temperature is 180~240 DEG C, and continuation mixing time is 1~2h.
3. a kind of preparation method of high strength starch plastics according to claim 1, it is characterised in that：Step
（2）The whipping temp is 75~85 DEG C, and mixing time is 1~2h, and cooling temperature is 35~45 DEG C, the mass fraction of hydrochloric acid
For 5%, the pH value of gelatinized corn starch liquid is adjusted as 4~6, and hydrolysis temperature is 28~36 DEG C, and enzymolysis time is 45~55min, hydroxide
The mass fraction of sodium solution is 4%, and it is 35~45 DEG C that temperature, which is mixed, and the mixing time is 24~32min, continues to stir
Time is 50~60min.
4. a kind of preparation method of high strength starch plastics according to claim 1, it is characterised in that：Step
（3）The fusion temperature is 1200~1600 DEG C, and fusing time is 12~16min, and wire drawing rotating speed is 100~200r/min,
The mass ratio for making glass fibre and cobweb by oneself is 1：2, soaking time is 1~2h.
5. a kind of preparation method of high strength starch plastics according to claim 1, it is characterised in that：Step
（4）The meter in parts by weight weighs 30~40 parts of modified polypropenes, 20~30 parts of modified self-control starch, 10~12 respectively
Part modified mixture, 4~6 parts of glycerine and 3~5 parts of atoleines, time of repose are 2~4h, and melting temperature is 160~240 DEG C,
Mixing time is 1~3h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111675849A (en) * | 2020-07-23 | 2020-09-18 | 上海方之德新材料有限公司 | Low-smoke halogen-free flame-retardant polyolefin microbeam tube cable material easy to tear by hand |
| CN113561538A (en) * | 2021-08-17 | 2021-10-29 | 高华文 | Manufacturing method of degradable button |
| CN114015125A (en) * | 2021-10-20 | 2022-02-08 | 界首市天鸿新材料股份有限公司 | Preparation method of antistatic biodegradable packaging film |
| CN114907622A (en) * | 2022-04-24 | 2022-08-16 | 宁波能之光新材料科技股份有限公司 | High-performance plasticized starch and preparation process thereof |
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| CN114015125A (en) * | 2021-10-20 | 2022-02-08 | 界首市天鸿新材料股份有限公司 | Preparation method of antistatic biodegradable packaging film |
| CN114015125B (en) * | 2021-10-20 | 2022-09-09 | 界首市天鸿新材料股份有限公司 | Preparation method of antistatic biodegradable packaging film |
| CN114907622A (en) * | 2022-04-24 | 2022-08-16 | 宁波能之光新材料科技股份有限公司 | High-performance plasticized starch and preparation process thereof |
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