CN103467887B - The preparation method of a kind of PVC castor oil-base carboxylate radical intercalated houghite and composite thermal stabilizer thereof - Google Patents
The preparation method of a kind of PVC castor oil-base carboxylate radical intercalated houghite and composite thermal stabilizer thereof Download PDFInfo
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Abstract
A preparation method for PVC castor oil-base carboxylate radical intercalated houghite and composite thermal stabilizer thereof, belongs to additives for plastics preparation and applied technical field thereof.The present invention adopts " calcine-recovering method ", castor oil-base carboxylate radical is inserted hydrotalcite layers, has prepared castor oil-base carboxylate radical intercalated houghite.Prepared castor oil-base carboxylate radical intercalated houghite has excellent thermal stability, and as auxiliary heat stabilizer, it is better than carbonate intercalated houghite to the improvement effect of calcium stearate/Zinic stearas system.As long-term thermal stability agent, at 180 DEG C, the static heat of Viscotrol C acid group intercalated houghite, toxilic acid polyricinoleate carboxylate radical intercalated houghite and hexahydrophthalic acid polyricinoleate carboxylate radical intercalated houghite is respectively steady time: 87.7 minutes, 68.4 minutes and 63.6 minutes, be better than 37.9 minutes of calcium stearate, long-term thermal stability performance is more better than calcium stearate.Equal safety and environmental protection, nontoxic, pollution-free from raw material to product.
Description
Technical field
The present invention relates to the preparation method of a kind of PVC castor oil-base carboxylate radical intercalated houghite and composite thermal stabilizer thereof, belong to additives for plastics preparations and applicatio technical field.
Background technology
Polyvinyl chloride (PVC) is second largest resins for universal use in the world, owing to there is the textural defect such as chlorallylene in PVC molecule, cause the thermal stability in its processing and moulding process poor, therefore, thermo-stabilizer need be added, to alleviate its thermal destruction when processing treatment.At present, thermo-stabilizer various in style, but great majority also exist the problems such as poisonous, expensive or harm environment.Therefore, develop a kind of thermo-stabilizer that is functional, cheap, safety and environmental protection to be significant.
Hydrotalcite-like material (LDHs) is anion type laminated compound, and interlayer has tradable negatively charged ion, is a kind of tool efficient, non-toxic heat stabilizer with broad prospects for development.LDHs is the lamellar compound be made up of metal hydroxides and the interlayer anion of positively charged of a class synthetic, and its composition general formula is: [M
2+ 1-X: M
3+ x(OH)
2] [A
m- x/mnH
2o] wherein M
2+, M
3+be respectively the metallic cation of divalent and 3 valencys, A
m-for interlayer anion.Hydrotalcite-based compound structure is unique, has the features such as memory effect, the interchangeability of interlayer anion and microvoid structure specific surface area are large.Can be applicable to fire-retardant, the aspect such as medical science, functional high molecule material.
Bioenergy has renewable, that other resources such as aboundresources, safety and environmental protection are incomparable advantage.China is one of major country of Castor and production castor seeds in the world, ricinolic acid wide material sources.Castor oil-base carboxylate radical is inserted hydrotalcite layers, not only can make full use of the abundant ricinolic acid resource of China, also provide new approach for new type water talcs thermo-stabilizer Application and Development.
Application number is the patent of 201010235534.4, discloses a kind of sulphur metaantimmonic acid root intercalated houghite and preparation method thereof, have raw material sources extensively, technical process and the advantage such as principle is simple.But need logical nitrogen in its building-up process, make technique comparatively complicated.
Castor oil-base carboxylate radical intercalated houghite prepared by the present invention, when taking into account long-term thermal stability, have excellent initial stage thermostability, and intercalation raw material used is mainly derived from vegetables oil, not containing heavy metal, and safety and environmental protection.Itself and conventional thermo-stabilizer are re-dubbed composite thermal stabilizer, and the thermostability of composite thermal stabilizer is higher, and at 180 DEG C, the thermal ageing Oven Method initial stage whiteness hold-time is up to more than 100min.
Summary of the invention
The technical problem that the object of the invention is to solve is the defect overcoming currently available products existence, provide a kind of environmental protection, nontoxic, efficient castor oil-base carboxylate radical intercalated houghite composite thermal stabilizer and preparation method thereof, the shortcomings such as to absorb HCl slow for overcoming existing hydrotalcite thermo-stabilizer, and the complicated and initial performances of synthesis technique is undesirable.
In order to solve the problems of the technologies described above, the invention provides following technical scheme:
A kind of preparation method of PVC castor oil-base carboxylate radical intercalated houghite is:
(1) in the castor oil-base organic acid or alcohol ester of 2 ~ 18g, add 100mL and remove CO
2deionized water, regulate this pH value of solution with dilute acid soln, make pH value of solution=4 ~ 6.
(2) calcined by ortho-water talcum, calcining temperature is 400 ~ 600 DEG C, and temperature rise rate is 4 ~ 10 DEG C/min, and calcination time is 3 ~ 7h.
(3) hydrotalcite after 3 ~ 24g being calcined, join in step (1) gained castor oil-base organic acid or alcohol ester solution, control temperature of reaction be 80 ~ 160 DEG C, the reaction times is 2 ~ 12h, reaction product after filtration, washing and drying after namely obtain castor oil-base carboxylate radical intercalated houghite.
Further, adjustment pH acid used is one or more mixtures in nitric acid, hydrochloric acid, sulfuric acid etc.
Further, described ortho-water talcum is business or homemade common ortho-water talcum, as one or more mixtures in carbonate form, nitric acid root type, sulfuric acid root type or chlorion type etc.
Further, described castor oil-base organic acid or alcohol ester are any one or two or more mixture in ricinolic acid, toxilic acid polyricinoleate, hexahydrophthalic acid polyricinoleate etc., and the general structure of castor oil-base organic acid or alcohol ester is as follows:
Further, consisting of of the composite thermal stabilizer of PVC castor oil-base carboxylate radical intercalated houghite: metal-salt, castor oil-base carboxylate radical intercalated houghite, business's (work) industry hydrotalcite, auxiliary heat stabilizer and oxidation inhibitor etc., wherein castor oil-base carboxylate radical intercalated houghite accounts for 10% ~ 30% of composite thermal stabilizer quality.
Further, described metal-salt be calcium stearate/zinc, glycerine calcium/zinc or any one or the two or more mixture crossed in the metal-salts such as alkali formula fatty acid calcium/zinc.
Further, auxiliary heat stabilizer used is any one or the two or more mixture in beta-diketon, phosphorous acid ester, epoxy soybean oil or polyvalent alcohol etc.
Beneficial effect of the present invention: castor oil-base organic carboxyl acid root intercalated houghite prepared by the present invention, has excellent thermal stability, and as auxiliary heat stabilizer, it is better than carbonate intercalated houghite to the improvement effect of calcium stearate/Zinic stearas system.As long-term thermal stability agent, long-term thermal stability performance is better than traditional calcium stearate.Castor oil-base carboxylate radical intercalated houghite composite thermal stabilizer after composite, at 180 DEG C, the thermal ageing Oven Method initial stage whiteness hold-time is up to more than 100min.And its intercalation raw material is mainly derived from reproducible vegetables oil, not containing heavy metal, asepsis environment-protecting.
Accompanying drawing explanation
X-ray diffraction (XRD) collection of illustrative plates of Fig. 1 castor oil-base carboxylate radical intercalated houghite.A: carbanion intercalated houghite; B: carbanion intercalated houghite calcinate; C: toxilic acid polyricinoleate carboxylate radical intercalated houghite; D: hexahydrophthalic acid polyricinoleate carboxylate radical intercalated houghite; E: castor oil-base carboxylate radical intercalated houghite.
Infrared (IR) collection of illustrative plates of Fig. 2 castor oil-base carboxylate radical intercalated houghite.A: carbanion intercalated houghite; B: castor oil-base carboxylate radical intercalated houghite; C: toxilic acid polyricinoleate carboxylate radical intercalated houghite; D: hexahydrophthalic acid polyricinoleate carboxylate radical intercalated houghite.
Fig. 3, at 180 DEG C, adds the colour-change of PVC test piece with thermal aging time of different thermo-stabilizer.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
Embodiment 1:
The preparation of Viscotrol C acid group intercalated houghite
(1) in the ricinolic acid of 7.71g, add 100mL and remove CO
2deionized water, with dust technology regulator solution pH, make pH value of solution=4 ~ 6.
(2) calcined by ortho-water talcum, calcining temperature is 450 DEG C, and temperature rise rate is 4 DEG C/min, and calcination time is 5h.
(3) by 3.95g calcine after hydrotalcite, join in above-mentioned ricinolic acid solution, control temperature of reaction be 135 DEG C, the reaction times is 6h, reaction product after filtration, washing and drying after namely obtain Viscotrol C acid group intercalated houghite, be designated as LDHs-RA.
Embodiment 2:
The preparation of toxilic acid ricinoleate ester carboxylate radical intercalated houghite
(1) by 68.62g ricinolic acid and 21.58g maleic anhydride, join in the 250mL there-necked flask with prolong and stir.Be warming up to 90 DEG C, reaction 3.5h, obtains toxilic acid ricinoleate ester, is designated as RAM.
(2) in the RAM of 4.51g, add 100mL and remove CO
2deionized water, with dust technology regulator solution pH, make pH value of solution=4 ~ 6.
(3) calcined by ortho-water talcum, calcining temperature is 450 DEG C, and temperature rise rate is 4 DEG C/min, and calcination time is 5h.
(4) hydrotalcite after 7.89g being calcined, join in above-mentioned toxilic acid ricinoleyl alcohol ester solution, controlling temperature of reaction is 135 DEG C, and the reaction times is 7h, reaction product after filtration, washing and drying after namely obtain toxilic acid ricinoleate ester carboxylate radical intercalated houghite, be designated as LDHs-RAM.
Embodiment 3:
The preparation of hexahydrophthalic acid polyricinoleate carboxylate radical intercalated houghite
(1) by 68.62g ricinolic acid and 33.92g HHPA, join in the 250mL there-necked flask with prolong and stir.Be warming up to 100 DEG C, reaction 3.5h, obtains hexahydrophthalic acid polyricinoleate, is designated as RAH.
(2) in the RAH of 3.47g, add 100mL and remove CO
2deionized water, with dust technology regulator solution pH, make pH value of solution=4 ~ 6.
(3) calcined by ortho-water talcum, calcining temperature is 450 DEG C, and temperature rise rate is 4 DEG C/min, and calcination time is 5h.
(4) hydrotalcite after 5.26g being calcined, join in above-mentioned hexahydrophthalic acid ricinoleyl alcohol ester solution, controlling temperature of reaction is 135 DEG C, reaction times is 7h, reaction product after filtration, washing and drying after namely obtain hexahydrophthalic acid polyricinoleate carboxylate radical intercalated houghite, be designated as LDHs-RAH.
Prepared LDHs-RA, LDHs-RAM and LDHs-RAH interlamellar spacing is respectively 1.6318nm, 2.3633nm and 2.2500nm, much larger than the 0.7667nm of carbonate intercalated houghite (being designated as LDHs), make castor oil-base carboxylate radical intercalated houghite for LDHs, more easily absorb HCl, the initial stage thermal stability of PVC test piece is improved.
Embodiment 4:
According to the composite thermal stabilizer of following formulating of recipe PVC castor oil-base carboxylate radical intercalated houghite
1# formula number (quality)
Zinic stearas 0.75
Viscotrol C acid group intercalated houghite 1.5
Carbonate intercalated houghite 0.75
Oxidation inhibitor (western Neil ST-76) 0.3
Epoxy soybean oil 1.5
Beta-diketon (western Neil SF-50) 0.2.
2# formula number (quality)
Zinic stearas 0.6
Toxilic acid polyricinoleate carboxylate radical intercalated houghite 1.2
Carbonate intercalated houghite 1.2
Oxidation inhibitor (western Neil ST-76) 0.3
Epoxy soybean oil 1.5
Beta-diketon (western Neil SF-50) 0.2
3# formula number (quality)
Zinic stearas 0.6
Hexahydrophthalic acid polyricinoleate carboxylate radical intercalated houghite 0.6
Carbonate intercalated houghite 1.8
Oxidation inhibitor (western Neil ST-76) 0.3
Epoxy soybean oil 1.5
Beta-diketon (western Neil SF-50) 0.2
By the composite thermal stabilizer in 50 parts of PVC powder (SG-5), 50 parts of PVC paste resins (P-440), 50 parts of dioctyl terephthalates and 1# formula (or 2# formula, 3# formula), be prepared into the test piece that thickness is about 1mm, in 120 DEG C of baking ovens, plastify 20min, test for thermal stability.
As the XRD figure spectrum that Fig. 1 is castor oil-base carboxylate radical intercalated houghite.The technical grade magnesium aluminum-hydrotalcite of wherein A is LDHs to be intercalant anion be carbonate, its characteristic peak 003,006,009 and 110 fairly obvious.The XRD figure spectrum of the product LDO after being LDHs calcining as can be seen from B, hydrotalcite layered structure is destroyed.By " memory effect " that LDO is special, after each castor oil-base carboxylate radical intercalation is entered hydrotalcite, the product of gained all has hydrotalcite characteristic peak.And for LDHs, the characteristic peak of E is LDHs-RA, C to be LDHs-RAM and D be 003,006 and 009 of LDHs-RAH moves to low angle, shows that the length of each castor oil-base carboxylic acid ion is greater than carbanion.
Fig. 2 is the IR collection of illustrative plates of castor oil-base carboxylate radical intercalated houghite, and b is LDHs-RA, c be LDHs-RAM and d is in the spectrogram of LDHs-RAH, at 3016cm
-1left and right is the=charateristic avsorption band of C-H, 1679 ~ 1550cm
-1with 1420 ~ 1390cm
-1-COO respectively
-unsymmetrically and symmetrical stretching vibration peak, and at 650cm
-1there is the flexural vibration peak of Al-OH in left and right.These results suggest that, castor oil-base carboxylate radical intercalation is comparatively complete.
Fig. 3 represents that employing thermal ageing Oven Method is investigated at 180 DEG C, adds the colour-change of PVC test piece with thermal aging time of different thermo-stabilizer.By Oven Method photo (due to former be colour picture, the requirement of patent application can not be met, now represent with gray scale sheet Fig. 3) can learn, adding of 1# formula, 2# formula and 3# formula, make PVC test piece at 180 DEG C, initial stage whiteness and long-term thermal stability performance are greatly improved, and the whiteness hold-time at initial stage of 3# formula is up to more than 100min.
What more than enumerate is only 3 kinds of specific embodiments of the present invention.Obviously, the present invention is not limited to above embodiment, can also have a lot of distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
A kind of PVC castor oil-base carboxylate radical intercalated houghite thermo-stabilizer and preparation method thereof of the present invention, adopts " calcine-recovering method ", three kinds of castor oil-base carboxylic acids is inserted hydrotalcite layers, is prepared into three kinds of castor oil-base carboxylate radical intercalated houghites.After composite to the insertion of prepared castor oil-base carboxylic acid hydrotalcite and metal-salt, oxidation inhibitor and auxiliary heat stabilizer etc., the composite thermal stabilizer of the castor oil-base carboxylate radical intercalated houghite obtained, thermal stability is better, at 180 DEG C, thermal ageing Oven Method initial stage whiteness and long-term thermal stability performance are greatly improved, and at 180 DEG C the whiteness hold-time at initial stage up to more than 100min.
Claims (6)
1. a PVC preparation method for castor oil-base carboxylate radical intercalated houghite, is characterized in that preparation process is as follows:
(1) in the castor oil-base organic acid or alcohol ester of 2 ~ 18g, add 100mL and remove CO
2deionized water, with dilute acid soln regulator solution pH=4 ~ 6;
Described castor oil-base organic acid or alcohol ester are: any one or two or more mixture in ricinolic acid, toxilic acid polyricinoleate, hexahydrophthalic acid polyricinoleate;
(2) calcined by ortho-water talcum, calcining temperature is 400 ~ 600 DEG C, and temperature rise rate is 4 ~ 10 DEG C/min, and calcination time is 3 ~ 7h;
(3) hydrotalcite after 3 ~ 24g being calcined, join in step (1) gained castor oil-base organic acid or alcohol ester solution, control temperature of reaction be 80 ~ 160 DEG C, the reaction times is 2 ~ 12h, reaction product after filtration, washing and drying after namely obtain castor oil-base carboxylate radical intercalated houghite.
2. the preparation method of PVC castor oil-base carboxylate radical intercalated houghite according to claim 1, is characterized in that: adjustment pH acid used is one or more mixtures in nitric acid, hydrochloric acid, sulfuric acid.
3. the preparation method of PVC castor oil-base carboxylate radical intercalated houghite according to claim 1, is characterized in that: described ortho-water talcum is business or homemade common ortho-water talcum: one or more mixtures in carbonate form, nitric acid root type, sulfuric acid root type or chlorion type.
4. the PVC preparation method of the composite thermal stabilizer of castor oil-base carboxylate radical intercalated houghite, it is characterized in that the castor oil-base carboxylate radical intercalated houghite prepared by method described in claim 1 and conventional thermo-stabilizer to carry out composite, consisting of of the composite thermal stabilizer obtained: metal-salt, castor oil-base carboxylate radical intercalated houghite, service water talcum, auxiliary heat stabilizer and oxidation inhibitor; Wherein castor oil-base carboxylate radical intercalated houghite accounts for 10% ~ 30% of composite thermal stabilizer quality.
5. the preparation method of the composite thermal stabilizer of PVC castor oil-base carboxylate radical intercalated houghite according to claim 4, is characterized in that: described metal-salt is calcium stearate/zinc, glycerine calcium/zinc or any one or the two or more mixture crossed in alkali formula fatty acid calcium/zinc.
6. the preparation method of the composite thermal stabilizer of PVC castor oil-base carboxylate radical intercalated houghite according to claim 4, is characterized in that: described auxiliary heat stabilizer is any one or two or more mixture in beta-diketon, phosphorous acid ester, epoxy soybean oil or polyvalent alcohol.
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| CN105295249A (en) * | 2015-11-18 | 2016-02-03 | 安徽华塑股份有限公司 | Hydrotalcite-rare earth composite environmental protection stabilizer for PVC, and preparation method thereof |
| CN109851951B (en) * | 2019-02-18 | 2022-04-15 | 杭州凌洲塑胶科技有限公司 | PVC wood-plastic material |
| CN109825002B (en) * | 2019-02-18 | 2021-12-28 | 杭州凌洲塑胶科技有限公司 | PVC environment-friendly calcium-zinc stabilizer |
| CN115403830B (en) * | 2022-09-02 | 2023-10-27 | 鄂尔多斯市瀚博科技有限公司 | Preparation method of modified hydrotalcite for PVC heat stabilizer |
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| "纳米LDHs作为UPVC热稳定剂的研究";孟兆会;《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》;20061115(第11期);正文第46-47页以及49页 * |
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