CN1221762A

CN1221762A - High polymer masterbatch able to be biologically degraded, its products mfg. method

Info

Publication number: CN1221762A
Application number: CN 97125221
Authority: CN
Inventors: 李明德; 顾家振; 李羽豪; 胡振林; 马鸿飞; 蔡荣根
Original assignee: SANLIN DEGRADABLE RESIN PRODUCTS CO SHANGHAI
Current assignee: SANLIN DEGRADABLE RESIN PRODUCTS CO SHANGHAI
Priority date: 1997-12-30
Filing date: 1997-12-30
Publication date: 1999-07-07

Abstract

A process for preparing biodegradable high-polymer mother particles and making its products includes adding starch to high polymer such as PE, PVA and PS, further addition of compatible agent and degradating agent, mixing, extruding out to obtain mother particles, and blowing to form plastic film, or adding foamer to make foam board, net, tube, etc.

Description

The manufacture method of biodegradable high polymer masterbatch and goods thereof

The present invention relates to the manufacture method of a kind of biodegradable high polymer masterbatch and goods thereof, specially refer to a kind of biodegradable plastics wrapping material, relate in particular to film and the film article of a kind of biodegradable PE.PE, PVA, PS foaming shockproof cushioning material, PE, PVA, PS bubble pad and foaming plate and utensils for snack etc.

Gong Ying plastics in the market, the plastic wrapping of commodity and cushioning material, shopping bag, refuse bag, utensils for snack etc. all belong to the biological product that is difficult to degrade, the product of this difficult degraded is after use, except that partially recycled utilization again, major part is used the refuse tip landfill disposal, under this natural condition, needs just can decompose through about 200 years.Owing to use the amount of plastics to increase gradually, to such an extent as to form " white " public hazards, cause secular environmental pollution, influence the eubiosis.Given this plant situation, the superpolymer biodegradable has been done a large amount of research, change or add some material from Polymer Structure, it is biodegradable to urge it, receive certain effect, at application number is in 94117828.5 Chinese patents, adopt PS to add the method for starch, it is biodegradable to urge it, thereby make that biodegradable plastics goods range of application enlarges greatly, public hazards also greatly reduce, on the cost of raw material sources, goods, also applying of biodegradable product is affected.

The present invention selects another kind of superpolymer PE for use for solving the weak point that exists now, and PVA or PS also increase the loading level of starch, in the temperature of manufacture craft, make its operation more easy to control that descends, simultaneously, in mixing, add compatilizer, degradation accelerating agent etc. greatly increase biodegradability.

Biodegradable high polymer masterbatch of the present invention consist of superpolymer, starch, compatilizer, short degradation agents, its content is the superpolymer of 8%-70% weight, the starch of 15%～86% weight, the compatilizer of 4%～12% weight, the degradation accelerating agent of 2%-3% weight.

The starch that the present invention adopts is industrial starch, and its granularity is 100 orders-600 orders, is specially W-Gum, and potato starch and sweet potato starch can adopt wherein a kind of, two kinds or three kinds.

The compatilizer that the present invention adopts is a glycerine, sorbyl alcohol a kind of or two kinds, and glycerine is saponification glycerine or compound glycerin, sorbyl alcohol is solid-state or liquid sorbyl alcohol.

The degradation accelerating agent that the present invention adopts is an aluminium hydroxide, oxidized petroleum waves, vegetables oil, in the iron stearate a kind of, two kinds, three kinds or four kinds.

The vegetables oil that the present invention adopts is a softening agent, is again autoxidator.Vegetables oil is specially soybean oil, epoxy soybean oil, rapeseed oil a kind of or two kinds.

When the preparation biodegradable plastic base material, in preparation process, make starch dehydration modification, after the modification, the starch water content is in 0.5%～2.5% weight.

It is length-to-diameter ratio 32: 1-48 that the present invention selects equipment for use: 1 big L/D ratio response type cord wood twin screw extruder, its machining functions is as figure.

State in the use in the equipment granulation process, starch is after the plasticizing dehydration, and is compatible with superpolymer under high speed banburying and high speed shear power and compatilizer effect, makes biodegradable master batch or PP Pipe Compound.

Because the starch resistance toheat of industry is relatively poor, when processing temperature surpasses 200 ℃ charing can take place generally, therefore, the complete processing temperature amplitude that the present invention adopts is 80 ℃～185 ℃, has so both guaranteed that material fully plastifies, and guaranteed not charing of starch again.

Adopt the masterbatch or the PP Pipe Compound of the present invention's preparation, use length-to-diameter ratio 20: 1-30: 1 inflation film manufacturing machine can be made the Biodegradable film goods, as agricultural film, and food bag, packing bag, shopping bag, refuse bag etc.

Equally, adopt the masterbatch of the present invention's preparation and PP Pipe Compound to pass through foaming machine,, or adopt butane to add the AC whipping agent, can make biodegradable foaming plate, foam screen, foaming pipe, foaming plastic tableware or amortizing packaging material with butane or AC.

The present invention will be for a more detailed description in conjunction with following embodiment, and except other had explanation, the umber among the embodiment all referred to parts by weight.

Embodiment:

1. with 55 parts of PE, 35 parts of starch, 7 parts of glycerine-sorbyl alcohol mixtures, 2 parts of softening agent, 1 part of degradation accelerating agent mixture is through the forcing machine granulation, and temperature is controlled between 80 ℃-180 ℃, blow molding after the granulation, make goods each component content, technological temperature and physical properties of articles thereof are listed in the table 1.

2. with 59 parts of PS and 30 parts of starch, 8 parts of sorbyl alcohols or glycerine, 1 part of softening agent, 2 parts of degradation accelerating agent mixtures make biodegradable foaming product through the forcing machine granulation by foaming machine.Each organizes content, and technological temperature and physical properties of articles are listed in the table 1,

3. with 35 parts of PVA, 55 parts of starch, 7 parts of glycerine or sorbyl alcohol, 2.5 parts of softening agent and 0.5 part of degradation accelerating agent, blow molding after the granulation makes goods each component content, and technological temperature and physical properties of articles are listed in the table 1.

Table 1

Embodiment number	Component						Technological temperature	Intensity is MPa in length and breadth	Heatproof	Heavy burden height change %	Doubling is inferior	Other
	Component												PS	?PE	?PVA	Starch	Compatilizer	Softening agent	Degradation accelerating agent
	1	?55		?35	????7	????2							PS	?PE	?PVA	Starch	Compatilizer	Softening agent	Degradation accelerating agent	????1	?80-180	In length and breadth	????12 ????10	????80
2	1	?55		?35	????7	????2	?59		?30	????8	????1	????2	?90-180	In length and breadth	????16 ????12	????80	????8	10 non-crackings		????1	?80-180	In length and breadth	????12 ????10	????80
2	3		?35	?55	????7	????2.5	?59		?30	????8	????1	????2	?90-180	In length and breadth	????16 ????12	????80	????8	10 non-crackings		????0.5	?100-180	In length and breadth	????13 ????11	????80

By table 1 as seen,, have good physicals, can satisfy general operational requirement with embodiment 1, embodiment 2 and embodiment 3 prepared goods.

For biodegradable its degradation property of superpolymer product of the present invention, can use flat band method (laboratory method), composting process, zero-G test method or field environment degraded method of testing are checked its effect, and its method and result are as follows.

1. flat band method: press the ASTMG21-90 technological standard, test the biodegradability of test samples with flat band method, sample is cut into the test piece of 3CM * 3CM, places the culture medium flat plate central authorities that prepare in advance, spray certain density test organisms spore mixing suspension, cover lid, put 30 ℃ ± 1 ℃ of temperature, cultivated 28 days routine observation fungus breeding situation in the relative temperature 95% above thermostat container, and the classification record, the results are shown in Table 2.

Table 2

Numbering	The sample title	Mycelia breeding situation				Remarks
		Mycelia breeding situation				Remarks	7 days	14 days	21 days	28 days
		????1	Biological degradation PVA film article	????1	????2	????3-	7 days	14 days	21 days	28 days		????3
????2	????1	????1		????1	????2	????3-	????2	????3-	????3+			????3
????2	????1	????3		????1	????2	????2+	????2	????3-	????3+		????3

In the table: 0 grade: do not have the breeding vestige

1 grade: breeding vestige≤10%

2 grades: slightly breed 10%-30%

3 grades: medium breeding 30%-60%

4 grades: breed 60% or full shaded surface in a large number

2. composting process: biological degradation PE film sample is cut into 20CM * 15CM test piece, and measure its tensile strength, that level places 100CM length * 30CM behind the weight is wide * hole that 15CM is dark, cover domestic refuse above, measure temperature and soil moisture every day, sampling regularly detects rate of weight loss and intensity, and notes down, and the results are shown in table 3.

Table 3

The heap bury the time (my god)	Rate of weight loss (%)	Breaking tenacity (N)	Breaking ductility (%)
The heap bury the time (my god)	Rate of weight loss (%)	Breaking tenacity (N)	Breaking ductility (%)	????0	????0	????5.89	????254.31
????20	????13	????5.18	????209.14	????0	????0	????5.89	????254.31
????20	????13	????5.18	????209.14	????40	????29	????4.68	????116.72
????60	????44	????3.97	????67.28	????40	????29	????4.68	????116.72

By above-mentioned table 2, table 3 as seen, the discarded back of articles of biodegradable plastics material is in physical environment, and particularly in the landfill environment, microorganism growth is rapid, the rate of weight loss height, and strength degradation is fast, has good degradation effect.

3. weightless test method: biological degradation PS sample by the SO846-1978 requirement, after 56 days microbial culture, is recorded rate of weight loss such as table 4.

Table 4

The sample title	Testing method	Rate of weight loss %	Molecular-weight average rate of descent %
The sample title	Testing method	Rate of weight loss %	Molecular-weight average rate of descent %	Biological degradation PS goods	ISO846-1978 (56 days)	????12.10	????39.48

4. field environment degraded method of testing: biological degradation PE film, biological degradation PVA film, biological degradation PS goods are abandoned in physical environment, the appearance change after 90 days, Strength Changes, the molecular-weight average rate of descent sees Table 5.

Table 5

The sample title	Test condition	Fate	Appearance change	Strength degradation rate %	Molecular-weight average rate of descent %
The sample title	Test condition	Fate	Appearance change	Strength degradation rate %	Molecular-weight average rate of descent %	Biological degradation PE film	Open-air physical environment	????90	Cracking, attenuation	????32.21	????35.46
Biological degradation PVA film	The same	????90	Cracking, attenuation	????34.07	????37.72	Biological degradation PE film	Open-air physical environment	????90	Cracking, attenuation	????32.21	????35.46
Biological degradation PVA film	The same	????90	Cracking, attenuation	????34.07	????37.72	Biological degradation PS goods	The same	????90	Cracking, fragmentation	????81.13	????40.10

By the method for above-mentioned several tests as seen, biodegradable superpolymer goods of the present invention, in flat band method, began to degrade through seven days, reach 60% all around, its stretch breaking strength, breaking ductility increases with the fate that heap buries, and significantly descends, same weight-loss method also shows prolongation in time, and the molecular weight and molecular weight rate is also very obvious.So biodegradable superpolymer of the present invention has by biodegradable speed very fast, residue is less and be the powder shape, reduce " white " public hazards greatly, influence to environment is atomic, again because goods raw material sources of the present invention are easy, cost is low, thereby this biodegradable articles is very easily promoted.

Claims

1. biodegradable high polymer masterbatch and goods thereof are by PE, PS, PVA and starch and compatilizer, degradation accelerating agent is formed, and it is characterized in that PE, and PS, PVA content are 8%-70% weight, starch is 15%-86% weight, and compatilizer is a 4%-12% weight, and degradation accelerating agent is a 2%-3% weight;

2. a kind of biodegradable high polymer masterbatch according to claim 1 and goods thereof is characterized in that starch can use industrial starch, and as W-Gum, potato starch, a kind of or two kinds, three kinds in the sweet potato starch, its granularity is 100 orders-600 orders.

3. a kind of biodegradable high polymer masterbatch according to claim 1 and goods thereof when it is characterized in that PE or PS or PVA and starch are mixing, add a kind of or two kinds of mixtures in compatilizer saponification glycerine or the sorbyl alcohol.

4. a kind of biodegradable high polymer masterbatch according to claim 1 and goods thereof is characterized in that PE, and PS when PVA and starch are mixing, adds degradation accelerating agent, as vegetables oil, and aluminium hydroxide, oxidized petroleum waves, a kind of in the iron stearate, two kinds, three kinds or four kinds.

5. a kind of biodegradable masterbatch according to claim 1 and goods thereof is characterized in that can be made into biodegradable film article with this masterbatch, foaming shockproof cushioning material, bubble pad, foaming plate and utensils for snack goods.