CN102337012A - High-strength P34HB/long glass fiber composite material and preparation method thereof - Google Patents
High-strength P34HB/long glass fiber composite material and preparation method thereof Download PDFInfo
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- CN102337012A CN102337012A CN2011101902536A CN201110190253A CN102337012A CN 102337012 A CN102337012 A CN 102337012A CN 2011101902536 A CN2011101902536 A CN 2011101902536A CN 201110190253 A CN201110190253 A CN 201110190253A CN 102337012 A CN102337012 A CN 102337012A
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- p34hb
- glass fiber
- roving glass
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- coupling agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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Abstract
The invention provides a high-strength P34HB/long glass fiber composite material and a preparation method thereof. The composite material comprises the following raw materials in percentage by weight: 40-90% of P34HB, 0-3% of nucleating agent, 5-40% of long glass fiber, 0-30% of filler and 0-0.5% of coupling agent. The preparation method of the composite material comprises the following steps: the P34HB, the nucleating agent, the filler and the coupling agent are mixed in a high-speed mixing machine, the uniformly mixed raw materials are arranged into a charging hole of a double-screw extruder, the long glass fiber enters from a glass fiber port, the materials are melted, extruded and pelleted to obtain the high-strength P34HB/long glass fiber composite material with a biodegradation performance. The composite material is provided with floating fiber on the surface, has very high smoothness and mechanical strength, can be processed into injection molding products, extruded products, films and foam products in a conventional plastic processing method, and can largely replace petroleum-based plastics to be used in the fields of industry, agriculture, medical treatment, packaging and the like.
Description
Technical field
The present invention relates to the bioabsorbable polymer material technical field, particularly relate to a kind of HS P34HB/ roving glass fiber matrix material and preparation method thereof.
Background technology
In pioneer of technology's prize in 2010; Polyhydroxyalkanoate (the PHAs of U.S. Metabolix exploitation; Polyhydroxyalkanoates) the bio-based complete degradable plastic is gone into list with the Twitter glory that starts global boom, becomes the technology of representing the tool innovation in the whole world.
In the economic trade activity of global integration, many countries are to plastics setting " green technology barrier ", and bio-degradable plastics helps to break this trade barrier.In these materials, the bio-based polymer that particularly reproducible natural biomass resource such as differentiation such as starch, straw obtain has good Biodegradable, because abundant raw materials, its research and development obtain the attention of various countries especially.With respect to common petroleum base polymer, the bio-based polymer can reduce the 30%-50% consumption of petroleum resources, reduces the dependence of people to petroleum resources; In whole process of production, consume carbonic acid gas and water simultaneously, can reduce Carbon emission; The biodegradable polymer goods can with organic waste compost treatment together, compare the step of having saved the manual sorting with general plastic garbage, greatly facilitate refuse collection and processing.So, to analyze from the meaning of Sustainable development, the bio-based polymer of " come from nature, belong to nature " can satisfy the requirement of cleaning development, Green Development and Sustainable development fully.
PHAs is that most of bacteriums are in the nutriment poorness and under the abundant condition of carbon source; Carbon and energy are stored and the material that obtains with insoluble inclusion body form; It is widespread in nature; Now both can be directly synthetic by mikrobe, also can through transgenic technology with the genes involved grafting in plant, through phytosynthesis.
The application of PHAs is the new field that Materials science combines with bio-science.PHAs industrialization kind had for four generations at present.The first-generation is PHB (poly 3-hydroxy butyrate), and this material percent crystallinity is big, and spherocrystal is big, and fragility is big, is difficult to large-scale application.The s-generation is PHBV (poly 3-hydroxy butyrate/3-hydroxyl pentanoate copolymer), because the monomeric introducing of 3-hydroxyl valerate, the fragility of PHBV has reduced than PHB, but cost is high.The third generation is PHBHHx (a 3-butyric ester/3-hydroxycaproic acid ester copolymer), and its cost is still very high.The 4th generation was P34HB (poly 3-hydroxy butyrate/4 hydroxybutyric acid ester copolymer).The blank of a lot of product scopes has been filled up in P34HB operation at home; Really realized " sustainable, the degradable green of raw material "; The P34HB production cost drops to per kilogram below 20 yuan by 50 yuan of original per kilograms at present; On material property, also obtained important breakthrough, the toughness of material is better.P34HB has thermoplasticity; Can on general processing units, extrude as petroleum base polymers such as PP, PS and PET, forming process such as injection moulding, bottle blowing, thermoforming; Produce film, sheet material, tubing and various heat product and injection moulded products, this material that has development potentiality of P34HB is expected to substitute traditional polymer in many Application Areass.The P34HB structural formula is following:
P34HB is a kind of typical hemicrystalline superpolymer; The monomeric introducing of 4 hydroxybutyric acid ester has reduced the percent crystallinity of PHA; But the crystallization rate of while 4 hydroxybutyric acid ester monomeric introducing also reduction P34HB multipolymer; Pure P34HB usually needs tens or could accomplish crystallisation process more than twenties hours; The goods shaping time is longer during forming process, and tooling cost increases, and material easily post crystallization takes place when at room temperature depositing and causes that product size changes, degradation.The adding of nucleator will help the P34HB material and accelerate crystallization rate, increases crystal density, and impel fine grain sizeization, thereby shorten the shaping cycle of goods, and help to improve product properties.
On the other hand, the mechanical property of P34HB is not high, and mechanical strength is only close with isotatic polypropylene, has limited its use range.Be the basis with existing resin, researching and developing preparation fiber-reinforced thermoplastic resin matrix material through compounding technologys such as fiber reinforcement, organic-inorganic blend has become current material Development Trend.The ceramic that spun glass (GF) is a kind of low price, mechanical property is excellent; Each item performance of glass reinforced composite materials all can be largely increased; Interface modification effect through coupling agent simultaneously can make the interface of system soak into and the bonding reinforcement, further improves the comprehensive mechanical property of system.Therefore be that the matrix material that strengthens body occupies suitable vast scale with the spun glass in the research of fibre composite.Research shows that for polymeric matrix, roving glass fiber enhanced effect is superior to short glass fiber enhanced effect, and for example the tensile strength of roving glass fiber REINFORCED PET is 1.5 times of short glass fiber REINFORCED PET, and flexural strength is 1.4 times, and shock strength is 3 times.Strengthen P34HB through roving glass fiber and be expected to prepare the excellent matrix material of mechanical property.
Summary of the invention
The objective of the invention is provides a kind of HS P34HB/ roving glass fiber matrix material and preparation method thereof to the weak point that the P34HB mechanical strength is low, crystallization rate is slow.
The object of the invention can be realized through following technical scheme:
A kind of HS P34HB/ roving glass fiber matrix material, the weight percent component of this matrix material is:
P34HB：40-90
Roving glass fiber: 5-40
Nucleator: 0-3
Filler: 0-50
Coupling agent: 0-0.5.
Described roving glass fiber diameter is the 5-30 micron.
Described nucleator comprises that organic type of nucleator, particle diameter are smaller or equal in 10 microns the mineral-type nucleator more than one.
Described particle diameter comprises in MOX, inorganic salt, weak base, the clay more than one smaller or equal to 10 microns mineral-type nucleator; Organic type of nucleator comprises more than one in small molecules organic nucleating agent, the polymer organic nucleating agent.
Said MOX comprises more than one in SP 1, silicon-dioxide, zinc oxide, Natural manganese dioxide, aluminium sesquioxide, titanium oxide, the lanthanum trioxide; Said inorganic salt comprise more than one in carbonate, silicate, the phosphoric acid salt; Said weak base comprises more than one in white lake, Marinco H, the calcium hydroxide; Said clay comprises more than one in mica, talcum powder, polynite, the kaolin; Said small molecules organic nucleating agent comprises more than one in the salt, aromatic hydroxyl sulphonate, diamide, glucitols of organic monacid sodium salt, organic monacid sylvite, organic monacid calcium salt, organic monacid magnesium salts, organo phosphorous compounds; Said polymer organic nucleating agent comprises in an alkali metal salt, ionic polymer of polyester oligomer more than one.
Described filler comprises wherein more than one of silicate, carbonate and carbide, vitriol and sulfide, titanate, oxyhydroxide, oxide compound, clay.
Described coupling agent comprises more than one in titante coupling agent, the silane coupling agent.
Described titante coupling agent comprises more than one in isopropoxy three iso stearate titaniums, isopropoxy three (dioctylphosphoric acid ester) titanium, isopropoxy three (dioctyl pyrophosphate) titanium, two (dioctylphosphoric acid ester) ethylene titanate, two (dioctyl pyrophosphate) hydroxyethanoic acid titanium; Described silane coupling agent comprises γ-(2; 3 glycidoxies) oxypropyl trimethyl silane, ethylene methacrylic base silane, N; In N '-two (2-methyl-2 nitro propyl group)-1, bis(3-triethoxy silylpropyl)tetrasulfide, vinyltriethoxysilane, vinyl three (beta-methoxy-oxyethyl group) silane, methyl allyl acyloxypropyl trimethoxysilane, the quadrol Union carbide A-162 more than one.
The system preparation process of above-mentioned HS P34HB/ roving glass fiber matrix material may further comprise the steps:
(1) takes by weighing the weight percent component of above-mentioned matrix material according to weight percent;
(2) P34HB, nucleator, filler, coupling agent are mixed in high-speed mixer;
(3) the above-mentioned raw material that mixes is thrown in the twin screw extruder charging opening, roving glass fiber is got into by the glass mouth, material
Melt extrude, granulation obtains HS P34HB/ roving glass fiber matrix material, 140-180 ℃ of forcing machine extrusion temperature, screw speed 100-450r/min.
Compared with prior art, the invention has the beneficial effects as follows:
1. the HS P34HB/ roving glass fiber matrix material with biodegradability of the present invention's preparation can substitute petroleum base in a large number and substitute the use of petroleum-based plastics in fields such as industry, agricultural, medical treatment and packings in a large number, has broad application prospects.
2. the present invention has significantly improved the mechanical property of P34HB through the roving glass fiber enhancement.The use of nucleator can improve the crystallization rate of P34HB, and the use of filler can further reduce the cost of P34HB.It is not floating fine that the prepared glass of the present invention strengthens P34HB material product surface, has very high slickness.
3. to prepare process simple in the present invention, and production process is controlled.
Embodiment
Below in conjunction with embodiment enforcement of the present invention is described further, but enforcement of the present invention is not limited thereto.
Embodiment 1:
Raw material weight per-cent prescription is (%):
P34HB：100
Embodiment 2:
Raw material weight per-cent prescription is (%):
P34HB：87
Sorbyl alcohol dibenzyl ester: 3
Roving glass fiber: 10
Embodiment 3:
Raw material weight per-cent prescription is (%):
P34HB：59
6250 order kaolin: 1
Sodium Benzoate: 0.3
Roving glass fiber: 40
Embodiment 4:
Raw material weight per-cent prescription is (%):
P34HB：78
Surlyn 9950 (E.I.Du Pont Company's product): 2
Roving glass fiber: 20
Vinyltriethoxysilane: 0.3
Embodiment 5:
Raw material weight per-cent prescription is (%):
P34HB：64
SP 1: 1
Roving glass fiber: 5
Light calcium carbonate: 30
Isopropoxy three iso stearate titaniums: 0.5
Embodiment 6:
Raw material weight per-cent prescription is (%):
P34HB：40
The composite nucleating agent of white lake, lanthanum trioxide (2:1): 3
Roving glass fiber: 15
Methyl allyl acyloxypropyl trimethoxysilane: 0.5
Polynite: 27
Permanent white: 15
Example 1, example 2, example 3, example 4, example 5, routine 6 preparing methods are identical, as follows:
All feed composition (roving glass fiber is imported by forcing machine glass mouth) are put into high-speed mixer by said ratio mix,
The above-mentioned raw material that mixes is thrown in the twin screw extruder charging opening, and roving glass fiber is got into by the glass mouth, and material melt extrudes,
Granulation obtains HS P34HB/ roving glass fiber matrix material, 165 ℃ of forcing machine extrusion temperatures, screw speed 250r/min.
DSC testing method to a kind of HS P34HB/ roving glass fiber matrix material of embodiment gained is: get 7 ~ 8mg embodiment product at N
2Under the atmosphere protection, 20 ℃/min is warming up to 170 ℃ and stop 5min to eliminate thermal history in 170 ℃, reduces to-50 ℃ of its decrease temperature crystalline curves of record with 5 ℃/min, 10 ℃/min, 15 ℃/min, the rate of temperature fall of 20 ℃/min from 170 ℃ then.Thermal crystalline temperature, peak crystallization halfwidth are based on the DSC decrease temperature crystalline curve of 5 ℃/min; And obtain kinetics of crystallization data F (T) about the treatment process of non-isothermal Kinetics deeply with reference to will not; F (T) is more for a short time to be illustrated in that to reach the needed rate of cooling of certain percent crystallinity in the unit time (1min) more little, i.e. the quantitatively explanation crystallization rate of expecting of measuring and monitoring the growth of standing timber is fast more.The result sees examining report of the present invention..
Mechanics Performance Testing to a kind of HS P34HB/ roving glass fiber matrix material of embodiment gained is carried out according to relevant iso standard.The result sees the examining report of table 1..
Table 1
| Test event | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Tensile strength, MPa | 26 | 48 | 92 | 75 | 67 | 52 |
| Flexural strength, MPa | 46 | 63 | 103 | 98 | 70 | 56 |
| Modulus in flexure, MPa | 1412 | 2578 | 7879 | 6343 | 4577 | 5465 |
| Notched Izod impact strength, KJ/m 2 | 4 | 5.5 | 6.2 | 5.8 | 4.9 | 4.6 |
| Shao Shi D hardness | 79 | 81 | 86 | 82 | 86 | 89 |
| Vicat softening point, ℃ | 105 | 112 | 116 | 106 | 114 | 118 |
| The thermal crystalline temperature, ℃ | 78 | 107 | 104 | 97 | 96 | 110 |
| The peak crystallization halfwidth, ℃ | 12.5 | 6.1 | 6.7 | 7.4 | 7.5 | 5.9 |
| F(T),min | 22.9 | 7 | 7.8 | 8.6 | 8.7 | 6.7 |
Above-mentioned instance can be found out: the HS P34HB/ roving glass fiber matrix material of the present invention's preparation is under the situation that significantly reduces the P34HB use cost, and crystallization rate significantly improves, and material mechanical performance has reached the standard of engineering plastics.The present invention is to advancing this high-fall suitability for industrialized production of separating biological plastics of P34HB and in the use in fields such as industry, agricultural, medical treatment and packing, having very important practical sense.
Claims (9)
1. HS P34HB/ roving glass fiber matrix material is characterized in that the weight percent component of this matrix material is:
P34HB：40-90
Roving glass fiber: 5-40
Nucleator: 0-3
Filler: 0-50
Coupling agent: 0-0.5.
2. HS P34HB/ roving glass fiber matrix material according to claim 1 is characterized in that said roving glass fiber diameter is the 5-30 micron.
3. HS P34HB/ roving glass fiber matrix material according to claim 1 is characterized in that, described nucleator comprises that organic type of nucleator, particle diameter are smaller or equal in 10 microns the mineral-type nucleator more than one.
4. HS P34HB/ roving glass fiber matrix material according to claim 3 is characterized in that described particle diameter comprises in MOX, inorganic salt, weak base, the clay more than one smaller or equal to 10 microns mineral-type nucleator; Organic type of nucleator comprises more than one in small molecules organic nucleating agent, the polymer organic nucleating agent.
5. HS P34HB/ roving glass fiber matrix material according to claim 4 is characterized in that described MOX comprises more than one in SP 1, silicon-dioxide, zinc oxide, Natural manganese dioxide, aluminium sesquioxide, titanium oxide, the lanthanum trioxide; Described inorganic salt comprise more than one in carbonate, silicate, the phosphoric acid salt; Described weak base comprises more than one in white lake, Marinco H, the calcium hydroxide; Described clay comprises more than one in mica, talcum powder, polynite, the kaolin; Described small molecules organic nucleating agent comprises more than one in the salt, aromatic hydroxyl sulphonate, diamide, glucitols of organic monacid sodium salt, organic monacid sylvite, organic monacid calcium salt, organic monacid magnesium salts, organo phosphorous compounds; Described polymer organic nucleating agent comprises in an alkali metal salt, ionic polymer of polyester oligomer more than one.
6. HS P34HB/ roving glass fiber matrix material according to claim 1 is characterized in that described filler comprises more than one in silicate, carbonate and carbide, vitriol and sulfide, titanate, oxyhydroxide, oxide compound, the clay.
7. HS P34HB/ roving glass fiber matrix material according to claim 1 is characterized in that described coupling agent comprises more than one in titante coupling agent, the silane coupling agent.
8. HS P34HB/ roving glass fiber matrix material according to claim 7; It is characterized in that described titante coupling agent comprises more than one in isopropoxy three iso stearate titaniums, isopropoxy three (dioctylphosphoric acid ester) titanium, isopropoxy three (dioctyl pyrophosphate) titanium, two (dioctylphosphoric acid ester) ethylene titanate, two (dioctyl pyrophosphate) hydroxyethanoic acid titanium; Described silane coupling agent comprises γ-(2; 3 glycidoxies) oxypropyl trimethyl silane, ethylene methacrylic base silane, N; In N '-two (2-methyl-2 nitro propyl group)-1, bis(3-triethoxy silylpropyl)tetrasulfide, vinyltriethoxysilane, vinyl three (beta-methoxy-oxyethyl group) silane, methyl allyl acyloxypropyl trimethoxysilane, the quadrol Union carbide A-162 more than one.
9. the preparation method of the said HS P34HB/ roving glass fiber of claim 1 matrix material is characterized in that, may further comprise the steps:
(1) takes by weighing the weight percent component described in the claim 1 according to weight percent;
(2) P34HB, nucleator, filler, coupling agent are mixed;
(3) the above-mentioned raw material that mixes is thrown in the twin screw extruder charging opening, roving glass fiber is got into by the glass mouth, material
Melt extrude, granulation obtains HS P34HB/ roving glass fiber matrix material, 140-180 ℃ of forcing machine extrusion temperature, screw speed 100-450r/min.
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| CN2011101902536A CN102337012A (en) | 2011-07-08 | 2011-07-08 | High-strength P34HB/long glass fiber composite material and preparation method thereof |
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| CN2011101902536A CN102337012A (en) | 2011-07-08 | 2011-07-08 | High-strength P34HB/long glass fiber composite material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756014A (en) * | 2014-01-07 | 2014-04-30 | 合肥杰事杰新材料股份有限公司 | Application of zinc oxide as anti-floating fiber agent of glass fiber enhanced thermoplastic plastic and anti-floating fiber master batch with zinc oxide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11323116A (en) * | 1998-05-12 | 1999-11-26 | Mitsubishi Gas Chem Co Inc | Biodegradable molding material, biodegradable molded article, and molding method for the biodegradable molding material |
-
2011
- 2011-07-08 CN CN2011101902536A patent/CN102337012A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11323116A (en) * | 1998-05-12 | 1999-11-26 | Mitsubishi Gas Chem Co Inc | Biodegradable molding material, biodegradable molded article, and molding method for the biodegradable molding material |
Non-Patent Citations (1)
| Title |
|---|
| 《塑料科技》 20110531 张向南 聚3-羟基丁酸酯4-羟基丁酸酯性能研究 表5 1-9 第39卷, 第5期 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756014A (en) * | 2014-01-07 | 2014-04-30 | 合肥杰事杰新材料股份有限公司 | Application of zinc oxide as anti-floating fiber agent of glass fiber enhanced thermoplastic plastic and anti-floating fiber master batch with zinc oxide |
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Application publication date: 20120201 |