CN105085983A - Halogen-free synergistic flame retardant, preparation method and composite flame retardant - Google Patents
Halogen-free synergistic flame retardant, preparation method and composite flame retardant Download PDFInfo
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Abstract
The invention relates to a halogen-free synergistic flame retardant for polyamide plastic and a preparation technology. The synergistic flame retardant is a phytic acid metal precipitate which is obtained by taking phytic acid, metal salts and hydroxides or oxides as raw materials through coprecipiation. A composite flame retardant formed by the synergistic flame retardant and components containing phosphorus can serve as a halogen-free flame retardant and be used for flame-retardant modification of polyamide polymer materials. The synergistic flame retardant accounts for 0.5%-5% of the whole flame retardant by weight percentage and can significantly improve the flame retardant property and the mechanical properties of flame retardant materials. The synergistic flame retardant is free of halogen, high in flame retardant efficiency, easy to prepare and easy to industrialize.
Description
Technical field
The present invention relates to a kind of new synergistic flame retardant---phytic acid precipitated metal thing, preparation technology, and with the research of new composite flame-retardant agent synergistic Flameproof polyamide class flame retardant of plastic performance and mechanical property.
Background technology
The advantages such as polymeric amide is a kind of important engineering plastics, has specific tenacity high, corrosion-resistant, are widely used in building, aerospace and the engineering field such as electric.Along with the development of macromolecular material industry, polyamide-based engineering plastics are substituted metal material just more and more.Although polyamide-based plastics have above-mentioned advantage, because it has inflammableness, and a large amount of cigarette and toxic gas can be discharged when burning, during a large amount of use, great potential safety hazard can be caused.
When using polyamide-based plastics, usually fire retardant can be added to improve the anti-fire performance of material in base material.In all fire retardants, the flame retarding efficiency of halogenated flame retardant is very high, and worsens less to the mechanical property of material, but can not meet environmental requirement, has therefore been subject to the resistance of particularly EU countries of many countries.Expansion type flame retardant is as not high in polyphosphoric acid amine (APP) flame retarding efficiency, and resistance to migration is bad, and can cause severe exacerbation to material mechanical performance.The flame retarding efficiency of red phosphorus (RP) is higher, but when adopting red phosphorus to make fire retardant, exists inflammable and produce the problems such as phosphuret-(t)ed hydrogen, and can deepen the color of goods.As aluminum diethylphosphinate (AlPi) of greatest concern in phosphonium flame retardant and polyphosphoric acid melamine (MPP), same exist some shortcomings and make it apply to be restricted.The flame retarding efficiency of MPP is lower, when addition is 25wt.%, the vertical combustion grade of nylon can be made to reach V-0 level, and can have larger deterioration to the mechanical property of base material.The flame retarding efficiency of AlPi is higher, and worsens less to base material mechanical property, but with high costs due to it, therefore also makes it apply and is restricted.
The development of current flame retardant industry mainly contains both direction: one is the more high flame retardant agent of synthesizing new flame retarding efficiency, and two is add novel synergistic fire retardant, and the flame retarding efficiency of original flame-retardant system is improved.In synthesizing new fire retardant, the new fire retardant of synthesis is mainly the analogue of AlPi and MPP at present.In novel synergistic fire retardant, polynite, zinc borate and sepiolite etc. are subject to extensive concern.Wherein, polynite, particularly nanometer organic modification montmonrillonite, when composite with fire retardants such as AlPi, MPP, APP, can reduce the peak heat rate of release (PHRR) about 50% of base material, and can improve the mechanical property of fire retardant material a little.Zinc borate, when forming ternary synergistic system with AlPi and MPP, can improve condensed phase shielding effect, improves flame retarding efficiency.Sepiolite, as efficient synergist, when with AlPi synergistic, can improve the flame retarding efficiency of AlPi.In synergistic flame retardant, adding of several synergistic flame retardant all can make the flame retarding efficiency of the fire retardant of synergistic with it be improved, but except polynite can improve the mechanical property by fire retardant material a little, zinc borate and sepiolite are all without improving by the report of fire retardant material mechanical property.As the research of synergistic flame retardant, at present we have not been reported novel organic phosphonate.
Because fire retardant existing on market all more or less exists various shortcoming, as flame retarding efficiency is not high, worsen mechanical property, raw smoke which large etc., therefore, new and effective, environmental protection and the fire retardant of less deterioration mechanical property or fire retarding synergist become following Developing mainstream.
Phytic acid derives from extraction or the commercial synthesis of plant itself, can be used as grease oxidation inhibitor, foodstuff additive and water-softening agent etc., and itself is nontoxic, meets environmental requirement, and is renewable resources.As a kind of material of industrialization already, there is the advantages such as the large and price of output is low.Phytic acid and most of divalence and the above metal ion of divalence have very strong sequestering power, generate throw out.Phytic acid precipitated metal thing at high temperature can decompose generation inositol and phosphoric acid salt, its mysoinositol can have well one-tenth charcoal effect as char-forming agent, phosphoric acid salt energy catalysis carbon-forming and increase layer of charcoal mechanical property, therefore, phytic acid precipitated metal thing has the fire-retardant effect of enhancing condensed phase.
Summary of the invention
The object of this invention is to provide a kind of Halogen synergistic flame retardant of polyamide-based plastics, preparation method and composite flame-retardant agent, to coordinate existing phosphorus system or phosphorus-nitrogenated flame retardant to improve the flame retarding efficiency of existing fire retardant, while the flammability problems solving existing polyamide polymer, overcome the shortcoming that the existing fire retardant in market worsens body material mechanical property, reach and improve flame retardant properties, mechanical property and the triple requirement of environmental protection.
The Halogen synergistic flame retardant of polyamide plastics of the present invention, this synergistic flame retardant is with phytic acid (C
6h
6o
6h
6-m) [PO (OH)
2]
m(m=1-6) and metal sources be the phytic acid precipitated metal thing that raw material is obtained by co-precipitation, in this phytic acid precipitated metal thing, the weight percentage of each element is: carbon 6.67-24.16wt.%, phosphorus 10.23-24.63wt.%, metal 13.28-35.63wt.%; Wherein, the structural formula (1) of described phytic acid is as follows,
In structural formula (1), R
1, R
2, R
3, R
4, R
5, R
6whole group is-PO (OH)
2; Or R
1, R
2, R
3, R
4, R
5, R
6a group is had at least to be-PO (OH)
2, all the other groups are-OH.
In above-mentioned phytic acid precipitated metal thing, described metallic element is calcium, magnesium, manganese, iron, zinc, aluminium, nickel or copper etc.
The preparation method of above-mentioned Halogen synergistic flame retardant, take following steps: (1). be raw material with plant acid solution and metal sources, be add in reaction vessel at 1: 1-1: 6 by the mol ratio of phytate molecule and metallic element, add solvent, stirring heating, is obtained by reacting a large amount of precipitation at 25-80 DEG C of temperature; Then at this temperature Keep agitation heating 1-2 hour, with deionized water wash and vacuum filtration precipitation obtain solid product; Wherein, metal sources is metal-salt, metal base or metal oxide; (2). gained solid product is put into baking oven, dries to constant weight, obtain final product---phytic acid precipitated metal thing.
In step (1), described solvent is water or ethanol, and after adding solvent, the total amount of solvent and the mass ratio of phytic acid amount are 20: 0.8-1.2.This mass ratio is preferably 20: 1.In step (2), bake out temperature is 80-120 DEG C.
Described metal sources is one or more in calcium oxide, lime acetate, nitrocalcite, Calcium hydrogen carbonate, calcium hydroxide, magnesium acetate, Magnesium hydrogen carbonate, magnesium oxide, manganous acetate, manganous sulfate, Manganous chloride tetrahydrate, manganous nitrate, iron nitrate, ferric sulfate, iron(ic) chloride, zinc acetate, zinc sulfate, zinc oxide, Tai-Ace S 150, aluminum chloride, aluminum nitrate, aluminum oxide, aluminium hydroxide, nickelous acetate, copper sulfate and cupric nitrate.
Adopt above-mentioned Halogen synergistic flame retardant can make a kind of composite flame-retardant agent of polyamide plastics.This composite flame-retardant agent is by Halogen synergistic flame retardant---and phytic acid precipitated metal thing and phosphorus containg substances form, and both content is: Halogen synergistic flame retardant 5.9-16.7wt.%, phosphorus containg substances 83.3-94.1wt.%.
Wherein, described phosphorus containg substances is one or more compounds in aluminum diethylphosphinate (AlPi), polyphosphoric acid melamine (MPP), ammonium polyphosphate (APP) and red phosphorus (RP).
The Halogen synergistic flame retardant of polyamide plastics of the present invention---phytic acid precipitated metal thing, at high temperature can decompose and generate inositol and phosphoric acid salt, its mysoinositol can have well one-tenth charcoal effect as char-forming agent, phosphoric acid salt energy catalysis carbon-forming and increase layer of charcoal mechanical property, have and strengthen the fire-retardant effect of condensed phase.
U.Braun etc. have studied research zinc borate being added AlPi and MPP flame-retardant system flame-proof glass fibre reinforced plastic PA66.Research shows, when keeping total flame retardant amount constant (18wt.%), can promote the condensed phase shielding effect that AlPi and MPP synergistic produces, make to be brought up to 33.3% by the LOI value of fire retardant material from 28.2% after a small amount of zinc borate adds.Z.S.Zhan etc. report the research of the fire-retardant non-reinforced plastic PA66 of sepiolite synergistic AlPi.When total flame retardant amount is 10wt.% (AlPi
:sepiolite=97: time 3), the PA66 do not strengthened can reach UL94V-0 rank, and LOI value can reach 32.5%.Adding of synergistic flame retardant of the present invention can make the flame retarding efficiency of fire retardant composite with it be improved, but can not improve by the mechanical property of fire retardant material.Phytic acid precipitated metal thing of the present invention is when with other phosphorus system or phosphorus-nitrogenated flame retardant synergistic Flameproof polyamide class plastics, flame retardant properties can be significantly improved, significantly improve the mechanical property of fire retardant material simultaneously, overcome the shortcoming that the existing fire retardant in market worsens body material mechanical property, reach and improve flame retardant properties, mechanical property and the triple requirement of environmental protection.
Halogen synergistic flame retardant of the present invention and composite flame-retardant agent, may be used for the flame-retardant modified of the polyamide plasticss such as polyhexamethylene adipamide, polycaprolactam, nylon 612, polyhexamethylene sebacamide.When this synergistic flame retardant content is 0.5wt.%-5wt.%, when described composite flame-retardant agent add-on is 8wt.%-30wt.%, the vertical combustion grade of polyamide-based plastics can be made to reach UL94V-0, simultaneously, with do not add compared with this synergistic flame retardant, tensile strength improves 7.8-39.7%, and notched Izod impact strength improves 10.5-85.7%.
Synergistic flame retardant manufacture craft of the present invention is simple, is easy to suitability for industrialized production.
Embodiment
Further illustrate below in conjunction with specific embodiment.
Embodiment 1: add phytic acid 0.1mol (namely 132 grams of concentration is the phytic acid aqueous solution of 50wt.%) and four water magnesium acetate 0.6mol (128.7g) in reaction vessel, add deionized water 1000mL, be heated with stirring to 70 DEG C, and Keep agitation heats 2h at this temperature, obtains white precipitate.Precipitate with deionized water is washed, vacuum filtration, the sample obtained is put into baking oven and dry to constant weight in 90 DEG C, obtain phytic acid magnesium product.Results of elemental analyses is: Mg18.15wt.%, C9.13wt.%, H2.21wt.%, P23.48wt.%.
By preparation phytic acid magnesium and the composite synergistic flame retardant polyhexamethylene adipamide (PA66) of MPP, its flame retardant properties and mechanical experimental results as shown in table 1.
Table 1
Embodiment 2: add phytic acid 0.1mol (namely 132 grams of concentration is the phytic acid aqueous solution of 50wt.%) and aluminum sulfate octadecahydrate 0.2mol (133.2g) in reaction vessel, add deionized water 1000mL, at 25 DEG C, stir 1h, obtain white precipitate.Precipitate with deionized water is washed, vacuum filtration, the sample obtained is put into baking oven and dry to constant weight in 110 DEG C, finally obtain phytic acid aluminium product.Results of elemental analyses is: Al14.26wt.%, C9.43wt.%, H2.12wt.%, P24.63wt.%.
By preparation phytic acid aluminium and AlPi synergistic flame-retardant PA 66, its flame retardant properties and mechanical experimental results as shown in table 2.
Table 2
Embodiment 3: add phytic acid 0.1mol (namely 132g concentration is the phytic acid aqueous solution of 50wt.%) and anhydrous zinc acetate 0.6mol (110.1g) in reaction vessel, add deionized water 1000mL, be heated with stirring to 60 DEG C, and Keep agitation heats 2h at this temperature, obtains white precipitate.Precipitate with deionized water is washed, vacuum filtration, the sample obtained is put into baking oven and dry to constant weight in 80 DEG C, finally obtain PHYTIC ACID ZINC SALT product.Results of elemental analyses is: Zn35.63%, C6.67wt.%, H2.25wt.%, P17.86wt.%.By the PHYTIC ACID ZINC SALT of preparation and the composite synergistic flame-retardant PA 66 of AlPi and MPP, the mass ratio of AlPi and MPP is 2:1 (AlPi+MPP), and it is fire-retardant and mechanical property is as shown in table 3.
Table 3
Embodiment 4: add phytic acid 0.1mol (namely 52 grams of concentration are a 50wt.% phytic acid aqueous solution) and water lime acetate 0.1mol (17.6g) in reaction vessel, add ethanol 800mL, be heated with stirring to 50 DEG C, and Keep agitation heats 2h at this temperature, obtains white precipitate.Precipitate with deionized water is washed, vacuum filtration, the sample obtained is put into baking oven and dry to constant weight in 120 DEG C, finally obtain phytic acid ca product.Results of elemental analyses is: Ca13.28wt.%, C24.16wt.%, H2.14wt.%, P10.23wt.%.
By the phytic acid ca of preparation and the fire-retardant polycaprolactam of AlPi and MPP (AlPi+MPP) composite synergistic (PA6), the mass ratio of AlPi and MPP is 2:1, and it is fire-retardant and mechanical property is as shown in table 4.
Table 4
Embodiment 5: add phytic acid 0.51mol (namely 132 grams of concentration is the phytic acid aqueous solution of 50wt.%) and four water nickelous acetate 0.6mol (149.3g) in reaction vessel, add ethanol 1200mL, be heated with stirring to 50 DEG C, and Keep agitation heats 1.5h at this temperature, obtains greenish precipitate.Precipitate with deionized water is washed, vacuum filtration, the sample obtained is put into baking oven and dry to constant weight in 100 DEG C, finally obtain phytic acid nickel product.Results of elemental analyses is: Ni35.18wt.%, C7.20wt.%, H2.15wt.%, P18.63wt.%.
By the phytic acid nickel of preparation and the composite synergistic flame-retardant PA 66 of AlPi and MPP (AlPi+MPP), the mass ratio of AlPi and MPP is 2:1, and it is fire-retardant and mechanical property is as shown in table 5.
Table 5
Embodiment 6: add phytic acid 0.1mol (namely 132 grams of concentration is the phytic acid aqueous solution of 50wt.%) and nine water iron nitrate 0.6mol (161.6g) in reaction vessel, add deionized water 1200mL, be heated with stirring to 40 DEG C, and Keep agitation heats 1.5h at this temperature, obtains white precipitate.Precipitate with deionized water is washed, vacuum filtration, the sample obtained is put into baking oven and dry to constant weight in 80 DEG C, finally obtain phytic acid iron product.Results of elemental analyses is: Fe25.57wt.%, C8.27wt.%, H2.17wt.%, P21.28wt.%.
By preparation phytic acid iron and APP synergistic flame-proof PA 6, its flame retardant properties and mechanical property as shown in table 6.
Table 6
Embodiment 7: add phytic acid 0.1mol (namely 132 grams of concentration is the phytic acid aqueous solution of 50wt.%) and four water manganous acetate 0.6mol (147.0g) in reaction vessel, add deionized water 1000mL, be heated with stirring to 70 DEG C, and Keep agitation heats 2h at this temperature, obtain lightpink precipitation.Precipitate with deionized water is washed, vacuum filtration, the sample obtained is put into baking oven and dry to constant weight in 100 DEG C, finally obtain phytic acid manganese product.Results of elemental analyses is: Mn33.64wt.%, C7.24wt.%, H2.11wt.%, P18.95wt.%.
By preparation phytic acid manganese and RP synergistic flame-retardant PA 66, its flame retardant properties and mechanical property as shown in table 7.
Table 7
Embodiment 8: add phytic acid 0.1mol (namely 132 grams of concentration is the phytic acid aqueous solution of 50wt.%) and calcium oxide 0.1mol (5.6g), nitrocalcite 0.1mol (16.4g), manganous sulfate 0.1mol (15.1g), Manganous chloride tetrahydrate 0.1mol (12.6mol), zinc sulfate 0.1mol (16.1g), copper sulfate 0.1mol (16.0g) in reaction vessel, add deionized water 1000mL, be heated with stirring to 80 DEG C, and Keep agitation heats 2h at this temperature, is precipitated.Precipitate with deionized water is washed, vacuum filtration, the sample obtained is put into baking oven and dry to constant weight in 80 DEG C, finally obtain phytic acid precipitated metal thing.Results of elemental analyses is: Ca8.25wt.%, Mn11.38wt.%, Zn6.71wt.%, Cu6.58wt.%, C7.42wt.%, H2.13wt.%, P19.19wt.%.By gained phytic acid precipitated metal thing synergistic MPP flame-proof PA 6, its flame retardant properties and mechanical property as shown in table 8.
Table 8
Embodiment 9: add phytic acid 0.1mol (100g concentration is the 50wt.% aqueous solution) and Calcium hydrogen carbonate 0.1mol (16.2g), Magnesium hydrogen carbonate 0.1mol (13.6g), zinc oxide 0.1mol (8.1g) cupric nitrate 0.1mol (18.8g) in reaction vessel, add deionized water 1000mL, be heated with stirring to 45 DEG C, and Keep agitation heats 2h at this temperature, is precipitated.Precipitate with deionized water is washed, vacuum filtration, the sample obtained is put into baking oven and dry to constant weight in 85 DEG C, finally obtain corresponding phytic acid precipitated metal thing.Results of elemental analyses is: Ca5.83wt.%, Mg3.48wt.%, Zn9.44wt.%, Cu9.31wt.%, C10.48wt.%, H2.06wt.%, P18.05wt.%.By gained phytic acid precipitated metal thing synergistic AlPi flame-retardant PA 66, its flame retardant properties and mechanical property as shown in table 9.
Table 9
Embodiment 10: add phytic acid 0.1mol (132g concentration is the 50wt.% aqueous solution) and calcium hydroxide 0.1mol (7.4g), magnesium oxide 0.1mol (4.0g) manganous nitrate 0.1mol (17.9g) iron(ic) chloride 0.1mol (16.3g) aluminum chloride 0.1mol (13.4g) in reaction vessel, add deionized water 1100ml, be heated with stirring to 50 DEG C, and Keep agitation heats 2h at this temperature, is precipitated.Precipitate with deionized water is washed, vacuum filtration, the sample obtained is put into baking oven and dry to constant weight in 85 DEG C, finally obtain corresponding phytic acid precipitated metal thing.Results of elemental analyses is: Ca4.67wt.%, Mg2.79wt.%, Mn6.41wt.%, Fe6.53wt.%, Al3.12wt.%, C8.42wt.%, H2.06wt.%, P21.83wt.%.By the gained phytic acid precipitated metal thing fire-retardant nylon 612 of synergistic AlPi and MPP (PA612), the mass ratio of AlPi and MPP (AlPi+MPP) is 2:1, its flame retardant properties and mechanical property as shown in table 10.
Table 10
Embodiment 11: add phytic acid 0.1mol (132g concentration is the 50wt.% aqueous solution) and ferric sulfate 0.05mol (20.0g), aluminum nitrate 0.1mol (21.3g), aluminum oxide 0.05mol (5.1g), aluminium hydroxide 0.1mol (7.8g) in reaction vessel, add deionized water 1100ml, be heated with stirring to 45 DEG C, and Keep agitation heats 1.5h at this temperature, is precipitated.Precipitate with deionized water is washed, vacuum filtration, the sample obtained is put into baking oven and dry to constant weight in 90 DEG C, finally obtain phytic acid precipitated metal thing.Results of elemental analyses is: Fe7.08wt.%, Al10.29wt.%, C9.12wt.%, H2.09wt.%, P23.65wt.%.By the fire-retardant polyhexamethylene sebacamide (PA610) of gained phytic acid precipitated metal thing synergistic AlPi, its flame retardant properties and mechanical property as shown in table 11.
Table 11
Claims (8)
1. a Halogen synergistic flame retardant for polyamide plastics, this synergistic flame retardant is with phytic acid (C
6h
6o
6h
6-m) [PO (OH)
2]
m(m=1-6) and metal sources are the phytic acid precipitated metal thing that raw material is obtained by co-precipitation, in this phytic acid precipitated metal thing, the weight percentage of each element is: carbon 6.67-24.16wt.%, phosphorus 10.23-24.63wt.%, metal 13.28-35.63wt.%; Wherein, the structural formula (1) of described phytic acid is as follows,
In structural formula (1), R
1, R
2, R
3, R
4, R
5and R
6whole group is-PO (OH)
2; Or R
1, R
2, R
3, R
4, R
5and R
6a group is had at least to be-PO (OH)
2, all the other groups are-OH.
2. Halogen synergistic flame retardant as claimed in claim 1, is characterized in that: described metallic element is calcium, magnesium, manganese, iron, zinc, aluminium, nickel or copper.
3. the preparation method of Halogen synergistic flame retardant described in claim 1 or 2, is characterized in that taking following steps:
(1). be raw material with plant acid solution and metal sources, be that 1:1-1:6 adds in reaction vessel by the mol ratio of phytate molecule and metallic element, add solvent, stirring heating, at 25-80 DEG C of temperature, be obtained by reacting a large amount of precipitation; Then at this temperature Keep agitation heating 1-2 hours, with deionized water wash and vacuum filtration precipitation obtain solid product; Wherein, metal sources is metal-salt, metal base or metal oxide;
(2). gained solid product is put into baking oven, dries to constant weight, obtain final product---phytic acid precipitated metal thing.
4. preparation method as claimed in claim 3, it is characterized in that: in step (1), after adding solvent, the total amount of solvent and the mass ratio of phytic acid amount are 20:0.8-1.2, and described solvent is water or ethanol.
5. the preparation method as described in claim 3 or 4, is characterized in that: in step (2), bake out temperature is 80-120 DEG C.
6. the preparation method as described in claim 3 or 4, is characterized in that: described metal sources is one or more in calcium oxide, lime acetate, nitrocalcite, Calcium hydrogen carbonate, calcium hydroxide, magnesium acetate, Magnesium hydrogen carbonate, magnesium oxide, manganous acetate, manganous sulfate, Manganous chloride tetrahydrate, manganous nitrate, iron nitrate, ferric sulfate, iron(ic) chloride, zinc acetate, zinc sulfate, zinc oxide, Tai-Ace S 150, aluminum chloride, aluminum nitrate, aluminum oxide, aluminium hydroxide, nickelous acetate, copper sulfate and cupric nitrate.
7. the composite flame-retardant agent of a polyamide plastics, it is characterized in that: this composite flame-retardant agent is made up of Halogen synergistic flame retardant-phytic acid precipitated metal thing and phosphorus containg substances, both content is: Halogen synergistic flame retardant 5.9-16.7wt.%, phosphorus containg substances 83.3-94.1wt.%.
8. composite flame-retardant agent as claimed in claim 7, is characterized in that: described phosphorus containg substances is one or more compounds in aluminum diethylphosphinate (AlPi), polyphosphoric acid melamine (MPP), ammonium polyphosphate (APP) and red phosphorus (RP).
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847351A (en) * | 2005-04-13 | 2006-10-18 | 信越化学工业株式会社 | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same |
-
2015
- 2015-09-22 CN CN201510606943.3A patent/CN105085983A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847351A (en) * | 2005-04-13 | 2006-10-18 | 信越化学工业株式会社 | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same |
Non-Patent Citations (2)
| Title |
|---|
| 叶在荣等: "粗植酸钙的制备II·沉淀条件", 《贵州农学院学报》 * |
| 王小华: "用沉淀法减少植酸钙的含杂量", 《陕西粮油科技》 * |
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