CN103833739A - Calcium-zinc composite heat stabilizer and preparation method and application thereof - Google Patents

Calcium-zinc composite heat stabilizer and preparation method and application thereof Download PDF

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CN103833739A
CN103833739A CN201410031721.9A CN201410031721A CN103833739A CN 103833739 A CN103833739 A CN 103833739A CN 201410031721 A CN201410031721 A CN 201410031721A CN 103833739 A CN103833739 A CN 103833739A
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zinc
calcium
organic acid
heat stabilizer
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陈思
王旭
徐晓鹏
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Zhejiang University of Technology ZJUT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/32—Cyanuric acid; Isocyanuric acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts

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Abstract

The invention discloses a calcium-zinc composite heat stabilizer designed on the basis of novel organic acid zinc, which is composed of the following raw materials in parts by mass: 30-65 parts of organic acid zinc, 25-70 parts of calcium stearate, 5-10 parts of epoxy compound, 6-12 parts of urea derivative, 3-9 parts of phosphite ester compound, 5-12 parts of polyol monoester compound, 4-8 parts of beta-diketone and 5-10 parts of C12-C18 long-chain fatty acid; the calcium-zinc composite heat stabilizer disclosed by the invention is simple in preparation process and excellent in heat stability, and can be widely applied to the field of PVC processing.

Description

A kind of calcium-Zn composite heat stabilizer and preparation method thereof and application
(1) technical field
The invention belongs to field of high polymer material processing, be specifically related to a kind of good calcium-zinc heat stabilizer of thermal stability designing on novel organic acid zinc-base plinth, and preparation method thereof with application in polyvinyl chloride manufacture field.
(2) background technology
Polyvinyl chloride (PVC) is most widely used thermoplastic resin, is also second-biggest-in-the-world resins for universal use, and its output is only second to polyethylene.PVC has good mechanicalness, erosion resistance and anti chemical properties, and there is good insulating, difficult combustion and transparent advantages of higher, can be widely used in the fields such as Industrial buildings, agricultural, packing, electronics, weaving, daily necessities, aviation, machinery, transportation and government utility.But PVC thermal stability is poor, adds and must add man-hour thermo-stabilizer to prevent its degraded.At present conventional PVC stablizer has lead salts, organic tin, metal soap, organic stabilizer etc., this wherein lead salts because poisonous, have pollution to be gradually prohibited from using to environment; Although and organic tin thermo-stabilizer is effective, price, have the shortcomings such as peculiar smell also greatly to limit its popularization; Organic stabilizer is because stabilising effect is poor, cannot use separately, can only be used as auxiliary stabilizer.Calcium-zinc stabilizer is the generally acknowledged nontoxic pollution-free of current PVC processing industry, stablizer most with prospects as the most frequently used metal soap stablizer.
But traditional but can not meet application demand take Zinic stearas and calcium stearate as the thermal stability of the calcium-zinc stabilizer of main stabilizer, the shortcoming of this class stablizer is long term thermal stablizer weak effect, zinc easily occurs and burn.Although can be by adding the auxiliary stabilizers such as polyvalent alcohol, organophosphite, beta-diketon class, polynary ester class, sulfocompound, hydrotalcite, zeolites to improve its stabilising effect, effect is still limited, causes its range of application narrower.
The present invention is directed to above-mentioned technical barrier, utilize the green synthesis process of water as solvent, introduce and there is certain thermally-stabilised function and can suppress the organic acid (I) that zinc burns, synthesized novel organic acid zinc; And studied the synergy of the stablizers such as this organic acid zinc and calcium stearate, beta-diketon, epoxy compounds, polyvalent alcohol, uridylic, design and develop efficiently, the compound calcium-zinc stabilizer of organic acid zinc-base cheaply.
(3) summary of the invention
In order to solve the not good shortcoming of existing calcium-zinc composite stabilizer stability, the invention provides a kind of new calcium-Zn composite heat stabilizer, for PVC manufacture field.
To achieve these goals, the present invention adopts following technical scheme:
First the present invention provides a kind of organic acid zinc, and described organic acid zinc is made by the raw material of following mass parts: 12.3～56.8 parts of organic acids, 100～150 parts, water shown in 21.9～143.5 parts of metallic zinc compounds, formula (I); Described organic acid zinc makes as follows: all raw materials are placed in to reactor, uniform stirring, back flow reaction 2～5 hours, in reaction process, dripping alkaline solution makes pH value maintain 6～9, in the time that reaction no longer produces precipitation, be reaction and finish, be then cooled to room temperature, filter, filter cake distilled water wash, obtains described organic acid zinc after being dried;
Figure BDA0000460980490000021
In formula (I), X is oxygen or sulphur; R 1, R 2, R 3be the alkyl of H, C1～C6, the thiazolinyl of C1～C6, epoxy alkyl, phenyl or the hydroxybenzyl of C1～C6 independently of one another.
Organic acid zinc of the present invention, wherein said metallic zinc compound is the one in zinc oxide, zinc acetate, zinc nitrate, zinc sulfate or zinc chloride, or the one in their hydrates separately.
The preparation method of organic acid zinc of the present invention, wherein said alkaline solution is selected from aqueous sodium hydroxide solution, the aqueous sodium carbonate of 10wt%～20wt% or the sodium bicarbonate aqueous solution of 10wt%～20wt% that concentration is 10wt%～20wt%.
Organic acid zinc of the present invention preferably makes as follows: get 12.3～56.8 parts of organic acids, 100～150 parts, water shown in 21.9～143.5 parts of metallic zinc compounds, formula (I), in formula (I), X is oxygen or sulphur; R 1, R 2, R 3be the alkyl of H, C1～C6, the thiazolinyl of C1～C6, epoxy alkyl, phenyl or the hydroxybenzyl of C1～C6 independently of one another; All raw materials are placed in to reactor, uniform stirring, back flow reaction 2～5 hours, in reaction process, dripping alkaline solution makes pH value maintain 6～9, in the time that reaction no longer produces precipitation, be reaction and finish, be then cooled to room temperature, filter, filter cake distilled water wash, obtains described organic acid zinc after being dried; Described metallic zinc compound is the one in zinc oxide, zinc acetate, zinc nitrate, zinc sulfate or zinc chloride, or the one in their hydrates separately; Described alkaline solution is selected from aqueous sodium hydroxide solution, the aqueous sodium carbonate of 10wt%～20wt% or the sodium bicarbonate aqueous solution of 10wt%～20wt% that concentration is 10wt%～20wt%.
The present invention also provides a kind of calcium-Zn composite heat stabilizer containing organic acid zinc of the present invention, and described calcium-Zn composite heat stabilizer is made up of the raw material of following quality proportioning: 30～65 parts, organic acid zinc, 25～70 parts of calcium stearates, 5～10 parts of epoxy compoundss, 6～12 parts of urea derivativess, 3～9 parts of phosphite ester compounds, 5～12 parts of polyol monoesters compounds, 4～8 parts of beta-diketons, 5～10 parts of C12～C18 longer chain fatty acids; Described epoxy compounds is epoxy soybean oil, epoxy Trisun Oil R 80 or epoxy aliphatic acid methyl ester; Described urea derivatives is 6-amino uracil, wallantoin, vitamin B13 or phenylurea; Described phosphite ester compound is phosphorous acid benzene di-isooctyl, trisnonyl phenyl phosphite or phosphorous acid hexichol isodecyl ester; Described polyol monoesters compounds is the monoesters that polyvalent alcohol and C8～C18 longer chain fatty acid generation esterification generate, and described polyvalent alcohol is tetramethylolmethane, dipentaerythritol, glycerol or Sorbitol Powder; Preferably described polyol monoesters compounds is pentaerythritol monostearate, pentaerythritol monooleate, Sorbitol Powder monostearate or dipentaerythritol monostearate; Described beta-diketon is stearoyl benzoyl methane or diphenylpropane-1,3-dione(DPPO).
Further, calcium-Zn composite heat stabilizer of the present invention is made up of the raw material of following quality proportioning: 5～10 parts of 30～65 parts, organic acid zinc, 25～70 parts of calcium stearates, 5～10 parts of epoxy soybean oils, 6～12 parts of 6-amino uracils, 3～9 parts of trisnonyl phenyl phosphites, 5～12 parts of pentaerythritol monostearates, 4～8 parts of diphenylpropane-1,3-dione(DPPO)s and stearic acid.
Further again, calcium-Zn composite heat stabilizer of the present invention is made up of the raw material of following quality proportioning: 6～8 parts of 50～60 parts, organic acid zinc, 40～50 parts of calcium stearates, 5～6 parts of epoxy soybean oils, 6～8 parts of 6-amino uracils, 4～6 parts of trisnonyl phenyl phosphites, 10～12 parts of pentaerythritol monostearates, 4～6 parts of diphenylpropane-1,3-dione(DPPO)s and stearic acid.
Concrete, optimum, calcium-Zn composite heat stabilizer of the present invention is made up of the raw material of following quality proportioning: 6 parts of 60 parts, organic acid zinc, 40 parts of calcium stearates, 5 parts of epoxy soybean oils, 8 parts of 6-amino uracils, 5 parts of trisnonyl phenyl phosphites, 10 parts of pentaerythritol monostearates, 4 parts of diphenylpropane-1,3-dione(DPPO)s and stearic acid.
Calcium-Zn composite heat stabilizer of the present invention is prepared as follows: according to the quality proportioning of each raw material, organic acid zinc, calcium stearate, epoxy compounds, urea derivatives, phosphite ester compound, polyol monoesters compounds, beta-diketon and C12～C18 longer chain fatty acid are dropped into high mixer, stir and be warming up to 80～120 ℃, maintain speed 40～80r/min, stir 10～30min, obtain composite calcium zinc thermo-stabilizer.
Calcium-Zn composite heat stabilizer of the present invention can be applicable to PVC manufacture field, and the quality consumption proportion of described calcium-Zn composite heat stabilizer and PVC is 1～5:100.
Compared with prior art, the present invention has following beneficial effect:
1, the technique of the synthetic organic acid zinc of the present invention is simple, water is cooked solvent and without catalyzer, process energy consumption than traditional synthetic fatty acid zinc salt is low, step is few and pollution-free, reduces the cost of product, is more conducive to applying of calcium-zinc composite stabilizer of the present invention.
2, the present invention has good thermostable effect for the synthesis of the organic acid of zinc salt itself, and there is complexing zinc chloride and suppress the function that zinc burns, synthetic organic acid zinc has more efficient stabilization function with respect to common fatty acid zinc salt thus, and zinc burns phenomenon to postpone greatly.
3, when the present invention's urea derivatives auxiliary stabilizer used uses separately, also have and stablize effect preferably, also possess the ability of complexing zinc chloride simultaneously, particularly outstanding with the composite Use Limitation fruit of synthetic organic acid zinc of the present invention.
4, the function that polyvalent alcohol burns because of its complexing zinc chloride inhibition zinc, thus be used for calcium-zinc stabilizer as auxiliary stabilizer.But polyvalent alcohol and PVC consistency are poor, easily separate out and affect the use of PVC goods.The present invention's polyol monoesters used not only has multiple hydroxyls and has retained and suppress the function that zinc burns, and also has chain alkyl and PVC has excellent compatibility, has guaranteed that product has expanded product use range efficiently simultaneously.
(4) embodiment
Below by embodiment, technical scheme of the present invention is further described in detail, but protection scope of the present invention is not limited to this.
Embodiment 1～4:
Two water zinc acetate 21.9g, two (epoxypropyl) chlorinated isocyanurates 48.2g, water 150g are placed in to reactor, uniform stirring, back flow reaction 2 hours.In reaction process, drip mass concentration and be the pH that 10% sodium hydroxide solution regulates reaction mixture, make pH maintain 7.After reaction finishes, be cooled to room temperature, filter, distilled water wash for filter cake (200mL × 3), puts into convection oven, is drying to obtain product two (epoxypropyl) chlorinated isocyanurates zinc at 100 ℃.By two (epoxypropyl) the chlorinated isocyanurates zinc making and calcium stearate, various auxiliary stabilizer, feed intake by formula rate, and be uniformly mixed in high-speed mixer, stir and be warming up to 100 ℃, stirring velocity 60r/min, after stirring 10min, make composite calcium-zinc heat stabilizer of the present invention, the charging capacity of concrete each raw material is in table 1.
The raw material charging capacity of table 1 embodiment 1～4 composite calcium-zinc heat stabilizer
Raw material Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Two (epoxypropyl) chlorinated isocyanurates zinc 50g 55g 60g 65g
Calcium stearate 50g 45g 40g 35g
Vitamin B13 6g 12g 6g 12g
Epoxy soybean oil 8g 8g 8g 8g
Triphenyl phosphite 5g 5g 5g 5g
Diphenylpropane-1,3-dione(DPPO) 4g 4g 4g 4g
Tetramethylolmethane stearate monoesters 8g 8g 12g 12g
Stearic acid 5g 5g 5g 5g
Get the each 4g of stablizer of above-described embodiment 1～4 preparation, separately respectively with 100gPVC resin (SG-5), 30 parts of calcium carbonate, 2g lubricant are even in high-speed mixer and mixing, and 180 ℃ of roller temperature, on roll spacing 1mm double roll mill, plasticate in flakes, then pelletizing is filled in test tube, aging in 180 ℃ of oil baths, then measure static heat stability energy according to standard GB/T/D917.1-2002 congo red method, record heat-stable time, the results are shown in Table 2.
The heat-stable time of table 2 embodiment 1～4 and comparative example
Group Heat-stable time (min)
Embodiment 1 75.3
Embodiment 2 79.2
Embodiment 3 81.6
Embodiment 4 83.5
Comparative example 72.3
Embodiment 5～8:
Zinc Sulphate Heptahydrate 143.5g, cyanuric acid 38.7g, water 150g are placed in to reactor, uniform stirring, back flow reaction 2 hours.In reaction way, drip mass concentration and be the pH that 10% sodium hydroxide solution regulates reaction mixture, make pH maintain 9.After reaction finishes, be cooled to room temperature, filter, distilled water wash for filter cake (300mL × 3), puts into convection oven, the dry product alkali formula cyanuric acid zinc that obtains for 2 hours at 120 ℃.By the alkali formula cyanuric acid zinc making and calcium stearate, various auxiliary stabilizer, feed intake by formula rate, and be uniformly mixed in high-speed mixer, stirring is warming up to 100 ℃, stirring velocity 60r/min, after stirring 10min, make the composite calcium-zinc heat stabilizer the present invention relates to, the charging capacity of concrete each raw material is in table 3.
The raw material charging capacity of table 3 embodiment 5～8 composite calciums-zinc heat stabilizer
Raw material Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8
Alkali formula cyanuric acid zinc 40g 50g 60g 65g
Calcium stearate 60g 50g 40g 35g
6-amino uracil 6g 6g 8g 8g
Epoxy soybean oil 5g 5g 10g 10g
Triphenyl phosphite 5g 5g 5g 5g
Diphenylpropane-1,3-dione(DPPO) 4g 4g 4g 4g
Tetramethylolmethane stearate monoesters 8g 8g 8g 8g
Stearic acid 5g 5g 5g 5g
Get the each 4g of stablizer of above-described embodiment 5～8 preparations, separately respectively with 100gPVC resin (SG-5), 30g calcium carbonate, 2g lubricant are even in high-speed mixer and mixing, and 180 ℃ of roller temperature, on roll spacing 1mm double roll mill, plasticate in flakes, then pelletizing is filled in test tube, aging in 180 ℃ of oil baths, after measure static heat stability energy according to standard GB/T/D917.1-2002 congo red method, record heat-stable time, the results are shown in Table 4.
The heat-stable time of table 4 embodiment 5～8 and comparative example
Group Heat-stable time (min)
Embodiment 5 70.5
Embodiment 6 73.5
Embodiment 7 78.6
Embodiment 8 81.3
Comparative example 72.3
Comparative example:
Get commercially available calcium-zinc heat stabilizer (HCZ1086F, Zhejiang Hai Pudun novel material limited-liability company) 4g and 100gPVC resin (SG-5), 30g calcium carbonate, 2g lubricant are even in high-speed mixer and mixing, and 180 ℃ of roller temperature, on roll spacing 1mm double roll mill, plasticate in flakes, then pelletizing is filled in test tube, aging in 180 ℃ of oil baths, after measure static heat stability energy according to standard GB/T/D917.1-2002 congo red method, recording heat-stable time is 72.3min.
Above embodiment is only the more representational example of the present invention.Obviously, technical scheme of the present invention is not limited to above-described embodiment, can also have many variations.The variation that those of ordinary skill in the art directly derives from content disclosed by the invention, all should think protection scope of the present invention.

Claims (10)

1.一种有机酸锌，其特征在于所述的有机酸锌由如下质量份的原料制得：金属锌化合物21.9～143.5份、式（I）所示有机酸12.3～56.8份、水100～150份；所述的有机酸锌按如下方法制得：将所有的原料置于反应釜中，均匀搅拌，回流反应2～5小时，反应过程中滴加碱溶液使pH值维持在6～9，当反应不再产生沉淀时即为反应结束，然后冷却至室温，过滤，滤饼用蒸馏水洗涤，干燥后即得所述的有机酸锌；1. A zinc organic acid, characterized in that the zinc organic acid is prepared from the following raw materials in parts by mass: 21.9 to 143.5 parts of a metal zinc compound, 12.3 to 56.8 parts of an organic acid shown in formula (I), and 100 to 100 parts of water 150 parts; the zinc organic acid is prepared as follows: put all the raw materials in a reaction kettle, stir evenly, and reflux for 2 to 5 hours. During the reaction, add an alkaline solution dropwise to maintain the pH value at 6 to 9 , when the reaction no longer produces precipitation, the reaction is over, then cooled to room temperature, filtered, the filter cake washed with distilled water, and dried to obtain the zinc organic acid;
Figure FDA0000460980480000011
Figure FDA0000460980480000011
 式（I）中X为氧或硫；R1，R2，R3各自独立地为H、C1～C6的烷基、C1～C6的烯基、C1～C6的环氧烷基、苯基或羟基苄基。In formula (I), X is oxygen or sulfur; R 1 , R 2 , and R 3 are each independently H, C1-C6 alkyl, C1-C6 alkenyl, C1-C6 epoxyalkyl, phenyl or hydroxybenzyl. 2.如权利要求1所述的有机酸锌，其特征在于所述的金属锌化合物为氧化锌、乙酸锌、硝酸锌、硫酸锌或氯化锌中的一种，或是它们各自的水合物中的一种。2. organic acid zinc as claimed in claim 1, it is characterized in that described metal zinc compound is a kind of in zinc oxide, zinc acetate, zinc nitrate, zinc sulfate or zinc chloride, or their respective hydrates One of. 3.如权利要求1所述的有机酸锌，其特征在于所述的碱溶液选自浓度为10wt%～20wt%的氢氧化钠水溶液、10wt%～20wt%的碳酸钠水溶液或10wt%～20wt%的碳酸氢钠水溶液。3. organic acid zinc as claimed in claim 1, is characterized in that described alkali solution is selected from the sodium hydroxide aqueous solution that concentration is 10wt%～20wt%, the sodium carbonate aqueous solution of 10wt%～20wt% or 10wt%～20wt% % sodium bicarbonate solution. 4.一种含权利要求1所述的有机酸锌的钙-锌复合热稳定剂，其特征在于所述的钙-锌复合热稳定剂由如下质量配比的原料组成：有机酸锌30～65份、硬脂酸钙25～70份、环氧化合物5～10份、脲衍生物6～12份、亚磷酸酯类化合物3～9份、多元醇单酯类化合物5～12份、β-二酮4～8份、C12～C18长链脂肪酸5～10份；所述环氧化合物为环氧大豆油、环氧葵花油或环氧脂肪酸甲酯；所述脲衍生物为6-氨基尿嘧啶、尿囊素、乳清酸或苯基脲；所述亚磷酸酯类化合物为亚磷酸苯二异辛酯、亚磷酸三壬基苯酯或亚磷酸二苯异癸酯；所述多元醇单酯类化合物为多元醇与C8～C18长链脂肪酸发生酯化反应生成的单酯，所述多元醇为季戊四醇、双季戊四醇、丙三醇或山梨糖醇；所述β-二酮为硬脂酰苯甲酰甲烷或二苯甲酰甲烷。4. A calcium-zinc composite thermal stabilizer containing organic acid zinc according to claim 1, characterized in that said calcium-zinc composite thermal stabilizer is made up of raw materials with the following mass ratio: organic acid zinc 30～ 65 parts, 25-70 parts of calcium stearate, 5-10 parts of epoxy compounds, 6-12 parts of urea derivatives, 3-9 parts of phosphite compounds, 5-12 parts of polyol monoester compounds, β - 4-8 parts of diketone, 5-10 parts of C12-C18 long-chain fatty acid; the epoxy compound is epoxy soybean oil, epoxy sunflower oil or epoxy fatty acid methyl ester; the urea derivative is 6-amino Uracil, allantoin, orotic acid or phenylurea; the phosphite compound is phenylenedioctyl phosphite, trinonylphenyl phosphite or diphenylisodecyl phosphite; Alcohol monoesters are monoesters produced by the esterification of polyols and C8-C18 long-chain fatty acids, the polyols are pentaerythritol, dipentaerythritol, glycerol or sorbitol; the β-diketones are hard Fatty acylbenzoylmethane or dibenzoylmethane. 5.如权利要求4所述的钙-锌复合热稳定剂，其特征在于所述的多元醇单酯类化合物为季戊四醇单硬脂酸酯、季戊四醇单油酸酯、山梨糖醇单硬脂酸酯、或双季戊四醇单硬脂酸酯。5. calcium-zinc composite heat stabilizer as claimed in claim 4, is characterized in that described polyhydric alcohol monoester compound is pentaerythritol monostearate, pentaerythritol monooleate, sorbitol monostearate ester, or dipentaerythritol monostearate. 6.如权利要求5所述的钙-锌复合热稳定剂，其特征在于所述的钙-锌复合热稳定剂由如下质量配比的原料组成：有机酸锌30～65份、硬脂酸钙25～70份、环氧大豆油5～10份、6-氨基尿嘧啶6～12份、亚磷酸三壬基苯酯3～9份、季戊四醇单硬脂酸酯5～12份、二苯甲酰甲烷4～8份和硬脂酸5～10份。6. The calcium-zinc composite heat stabilizer as claimed in claim 5, characterized in that the calcium-zinc composite heat stabilizer is made up of the following mass ratio raw materials: 30-65 parts of organic acid zinc, stearic acid 25-70 parts of calcium, 5-10 parts of epoxidized soybean oil, 6-12 parts of 6-aminouracil, 3-9 parts of trinonylphenyl phosphite, 5-12 parts of pentaerythritol monostearate, diphenyl 4-8 parts of formylmethane and 5-10 parts of stearic acid. 7.如权利要求5所述的钙-锌复合热稳定剂，其特征在于所述的钙-锌复合热稳定剂由如下质量配比的原料组成：有机酸锌50～60份、硬脂酸钙40～50份、环氧大豆油5～6份、6-氨基尿嘧啶6～8份、亚磷酸三壬基苯酯4～6份、季戊四醇单硬脂酸酯10～12份、二苯甲酰甲烷4～6份和硬脂酸6～8份。7. The calcium-zinc composite heat stabilizer as claimed in claim 5, characterized in that the calcium-zinc composite heat stabilizer is made up of the following mass ratio raw materials: 50-60 parts of organic acid zinc, stearic acid 40-50 parts of calcium, 5-6 parts of epoxidized soybean oil, 6-8 parts of 6-aminouracil, 4-6 parts of trinonylphenyl phosphite, 10-12 parts of pentaerythritol monostearate, diphenyl 4-6 parts of formylmethane and 6-8 parts of stearic acid. 8.如权利要求5所述的钙-锌复合热稳定剂，其特征在于所述的钙-锌复合热稳定剂由如下质量配比的原料组成：有机酸锌60份、硬脂酸钙40份、环氧大豆油5份、6-氨基尿嘧啶8份、亚磷酸三壬基苯酯5份、季戊四醇单硬脂酸酯10份、二苯甲酰甲烷4份和硬脂酸6份。8. The calcium-zinc composite heat stabilizer as claimed in claim 5, characterized in that the calcium-zinc composite heat stabilizer is made up of the following mass ratio raw materials: 60 parts of organic acid zinc, 40 parts of calcium stearate 5 parts, 5 parts of epoxidized soybean oil, 8 parts of 6-aminouracil, 5 parts of trinonylphenyl phosphite, 10 parts of pentaerythritol monostearate, 4 parts of dibenzoylmethane and 6 parts of stearic acid. 9.如权利要求4～8之一所述的钙-锌复合热稳定剂，其特征在于，所述的有机酸锌按如下方法制得：取金属锌化合物21.9～143.5份、式（I）所示有机酸12.3～56.8份、水100～150份，式（I）中X为氧或硫；R1，R2，R3各自独立地为H、C1～C6的烷基、C1～C6的烯基、C1～C6的环氧烷基、苯基或羟基苄基；将所有的原料置于反应釜中，均匀搅拌，回流反应2～5小时，反应过程中滴加碱溶液使pH值维持在6～9，当反应不再产生沉淀时即为反应结束，然后冷却至室温，过滤，滤饼用蒸馏水洗涤，干燥后即得所述的有机酸锌；所述的金属锌化合物为氧化锌、乙酸锌、硝酸锌、硫酸锌或氯化锌中的一种，或是它们各自的水合物中的一种；所述的碱溶液选自浓度为10wt%～20wt%的氢氧化钠水溶液、10wt%～20wt%的碳酸钠水溶液或10wt%～20wt%的碳酸氢钠水溶液；9. The calcium-zinc composite heat stabilizer according to any one of claims 4 to 8, characterized in that the zinc organic acid is prepared as follows: take 21.9 to 143.5 parts of metal zinc compound, formula (I) 12.3-56.8 parts of organic acid shown, 100-150 parts of water, X in formula (I) is oxygen or sulfur; R 1 , R 2 , R 3 are each independently H, C1-C6 alkyl, C1-C6 alkenyl, C1-C6 epoxyalkyl, phenyl or hydroxybenzyl; put all the raw materials in the reaction kettle, stir evenly, and reflux for 2-5 hours. During the reaction, add alkali solution dropwise to make the pH Maintained at 6-9, when the reaction no longer produces precipitation, the reaction is over, then cooled to room temperature, filtered, the filter cake is washed with distilled water, and the organic acid zinc is obtained after drying; the metal zinc compound is oxidized One of zinc, zinc acetate, zinc nitrate, zinc sulfate or zinc chloride, or one of their respective hydrates; the alkali solution is selected from a concentration of 10wt% to 20wt% sodium hydroxide aqueous solution , 10wt% to 20wt% sodium carbonate aqueous solution or 10wt% to 20wt% sodium bicarbonate aqueous solution; 所述钙-锌复合热稳定剂按如下方法制备：按照各原料的质量配比，将有机酸锌、硬脂酸钙、环氧化合物、脲衍生物、亚磷酸酯类化合物、多元醇单酯类化合物、β-二酮和C12～C18长链脂肪酸投入高混机，搅拌并升温至80～120℃，维持速率40～80r/min，搅拌10～30min，即得复合钙锌热稳定剂。The calcium-zinc composite heat stabilizer is prepared as follows: according to the mass ratio of each raw material, organic acid zinc, calcium stearate, epoxy compound, urea derivative, phosphite compound, polyol monoester Put the compound, β-diketone and C12-C18 long-chain fatty acid into the high mixer, stir and raise the temperature to 80-120°C, maintain the speed of 40-80r/min, and stir for 10-30min to obtain the composite calcium-zinc heat stabilizer. 10.如权利要求4～8之一所述的钙-锌复合热稳定剂在PVC加工中的应用，其特征在于所述钙-锌复合热稳定剂与PVC的质量用量配比为1～5:100。10. The application of the calcium-zinc composite heat stabilizer as claimed in any one of claims 4 to 8 in PVC processing, characterized in that the mass dosage ratio of the calcium-zinc composite heat stabilizer to PVC is 1 to 5 :100.
CN201410031721.9A 2014-01-23 2014-01-23 Calcium-zinc composite heat stabilizer and preparation method and application thereof Pending CN103833739A (en)

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