CN100447204C - Environmental protective type liquid composite thermal stabilizer, and preparation method - Google Patents
Environmental protective type liquid composite thermal stabilizer, and preparation method Download PDFInfo
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- CN100447204C CN100447204C CNB2006101664325A CN200610166432A CN100447204C CN 100447204 C CN100447204 C CN 100447204C CN B2006101664325 A CNB2006101664325 A CN B2006101664325A CN 200610166432 A CN200610166432 A CN 200610166432A CN 100447204 C CN100447204 C CN 100447204C
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Abstract
This invention discloses a method for preparing environmentally friendly liquid composite thermal stabilizer, which is composed of: metal soap as the main thermal stabilizer, and auxiliary materials such as phosphite and epoxy soybean oil. The liquid composite thermal stabilizer has such advantages as high thermal stability and no toxicity, and is environmentally friendly. The thermal stability is higher than that of the present commercialized products.
Description
Technical field
A kind of environmental protective type liquid composite thermal stabilizer and preparation method thereof relates to a kind of Heat stability is good, nontoxic substantially liquid composite thermal stabilizer particularly, belongs to Minute Organic Synthesis and compounded technology field.
Background technology
Thermo-stabilizer is exclusively used in the processing of polrvinyl chloride product, prevent effectively in the course of processing owing to the degraded of being heated and the mechanical shearing effect causes, can also alleviate the PVC goods in use because the destruction that the effect of heat, light and oxygen is subjected to, prolong the work-ing life of goods.
In recent years, formed heat stabilizer system based on lead salt and metallic soap.But lead salt toxicity is big, and is seriously polluted, and it is comparatively loaded down with trivial details to prepare burden, and comprehensive cost is higher; And the metallic soap resource is also very limited.Especially the mid-1960s begins, world developed country particularly state such as America and Europe is fully recognized that the environmental problem that lead, cadmium etc. cause is serious day by day, thereby use plumbous, cadmium salt there has been very strict restriction, particularly safety problem such as food product pack, medical sanitary apparatus causes that people pay much attention to, impel thermo-stabilizer research along unleaded, no cadmium development, countries in the world are researched and developed the substitute of lead, cadmium stabilizer one after another, and the friendly nontoxic PVC stablizer of research and development novel environmental has become inexorable trend.
In addition, the metallic soap class also is most of poisonous, and nontoxic metallic soap class processing characteristics is bad again.Organic tin stablizer stabilising effect is good, nontoxic or low toxicity, but the higher uncomfortable China's national situation of price.Pure organic class stablizer effect steady in a long-term is bad, uses so generally can only make auxiliary stabilizer.Therefore developing compound stablizer seems very urgent.Simultaneously, China's rare earth resources is abundant, and is cheap, and rare-earth stabilizer has characteristic such as efficient, nontoxic and multi-functional, develops therefore that rare-earth stabilizer is with a wide range of applications and social benefit.
The heat of liquid stablizer has dustless, disperses easily during use, and is simple to operate, so development of new efficient liquid, non-toxic stabilizer makes the kind of stablizer abundanter, makes the processing of PVC easier, safer.
At present, organic acid all derives from petroleum resources mostly, and oil price rises steadily, and the price of stablizer certainly will fluctuate with this, and therefore, existing simultaneously also at consideration employing biomass material, both compliance with environmental protection requirements had been broken away from the restriction of oil again.It is one of organic acid raw material that the present invention adopts citric acid, and it is a polycarboxylic acid, and carboxyl is many more, and the metal ion of replacement is many more, can improve metal content greatly.
Summary of the invention
The object of the present invention is to provide a kind of environmental protective type liquid composite thermal stabilizer and preparation method thereof, solve the problem of above-mentioned existence, Heat stability is good, nontoxic substantially a kind of liquid composite thermal stabilizer preparation method and relevant measurement result are provided.
Technical scheme of the present invention: the component of this thermo-stabilizer is counted metallic soap 35%-50%, phosphorous acid ester 10%-25%, dihydroxyphenyl propane 1%-2%, epoxy soybean oil 5%-10%, mineral oil 15%-30% with the quality percentage, by the composite liquid composite thermal stabilizer that makes of proportioning; The general structure of metallic soap is: (RCOO)
xMe.
Acid group is the isocaprylic acid root in the general structure of metallic soap
The time, be isocaprylic acid series composite thermal stabilizer by the composite products obtained therefrom of proportioning.Acid is citric acid series in the general structure of metallic soap
Or
Me is calcium, zinc, barium, potassium or rare earth.R ' is an alkyl.
Preparation isocaprylic acid series composite thermal stabilizer:
(1) preparation metallic soap: reaction equation is:
MeO+RCOOH→(RCOO)
xMe+H
2O
A certain amount of isocaprylic acid, glycol ether, mineral oil are stirred, be warming up to 70 ℃～80 ℃, add metal oxide, isocaprylic acid: the metal oxide mol ratio is 1: 0.9～1.1, behind reaction 1h～1.5h, carry out decompression dehydration, be cooled to 50 ℃～60 ℃, carry out filtration under diminished pressure, promptly get isocaprylic acid series metal soap.
(2) compound heat stabilizer: dihydroxyphenyl propane is dissolved in phosphorous acid ester by proportioning, control 80-90 ℃, until its dissolving, add two or more isocaprylic acid metallic soaps, epoxy soybean oil and mineral oil then successively, stir constant temperature 1.5h～2h, be cooled to 50 ℃ of decompress filters, get light yellow transparent liquid, be isocaprylic acid series composite thermal stabilizer.
Preparation isocaprylic acid zinc metallic soap: isocaprylic acid: ZnO=1: 1～1.1, glycol ether consumption be the isocaprylic acid quality 3%～5%, the mineral oil consumption is 20%～25% of isocaprylic acid quality.
Or preparation calcium iso-octoate metallic soap: isocaprylic acid: CaO=1: 0.9～1, glycol ether consumption be the isocaprylic acid quality 13%～16%, the mineral oil consumption is 60%～80% of isocaprylic acid quality.
The used metallic soap of compound heat stabilizer is two kinds on calcium iso-octoate and an isocaprylic acid zinc, and the amount ratio of calcium iso-octoate and isocaprylic acid zinc is 1.5～2: 1.
Preparation citric acid series composite thermal stabilizer:
(1) preparation metallic soap:
Citric acid is dissolved in the distilled water, adds metal oxide under the normal temperature in batches, treat solid dissolving, 1h～2h is complete in reaction, and solution is filtered, and treats filtrate leaving standstill, and the adularescent material is separated out, filter, washing, oven dry, citric acid metal soap; The citric acid consumption is 0.4～0.5mol/L, and the metal oxide consumption is 0.1～0.2mol/L.
(2) compound heat stabilizer: in the four neck flasks of 250mL, dihydroxyphenyl propane is dissolved in phosphorous acid ester by proportioning, control 80-90 ℃, until its dissolving, add one or both citric acid metal soaps, epoxy soybean oil and mineral oil then successively, stir constant temperature 1.5h～2h, be cooled to 50 ℃ of decompress filters, get light yellow transparent liquid, be citric acid series composite thermal stabilizer.
The used metal oxide of preparation metallic soap is zinc oxide or calcium oxide, and the used citric acid metal of compound heat stabilizer soap is zinc citrate and/or citrate of lime.
At present, the safety problem of the plastic prod that contacts with human body receives much concern, and especially European Union member countries' strictness defines the toxic ingredient content of plastic prod.Irritate stomach method contamination method with calcium iso-octoate of the present invention/zinc composite stabilizer product through per os of Kunming mouse, measured acute toxic reaction and Lethal Dose 50 (LD50), for Secure Application provides parameter.Product is mixed with 25% the concentration of being tried with edible vegetable oil.Get 20 of healthy Kunming mouses, body weight 18～20g, male and female half and half, empty stomach 8h, per os is once irritated stomach, observes continuously 14 days.Animal chilly occurs, tiredly reduces movingly about 10min after irritating stomach, continue progressively to recover after about 2 hours, recovers fully behind the 24h, does not see other abnormal conditions, and animal dead is not arranged yet.Continue to observe 14 days, abnormal response does not appear in animal.Observation period finishes, and puts to death surviving animals and carries out gross anatomy, and the postmortem result does not see that naked eyes are as seen unusual.LD50＞the 5000mg/kg of stablizer product of the present invention belongs to nontoxic substantially.
Embodiment
Embodiment 1 preparation isocaprylic acid zinc soap
A certain amount of isocaprylic acid, glycol ether, mineral oil are stirred in the 270L reactor, be warming up to 70 ℃～80 ℃, add ZnO, behind reaction 1h～1.5h, carry out decompression dehydration, be cooled to 50 ℃～60 ℃, the flat panel filter machine leads to nitrogen filtering, gets clear, colorless liquid; Isocaprylic acid: ZnO=1: 1～1.1, glycol ether consumption be the isocaprylic acid quality 3%～5%, the mineral oil consumption is 20%～25% of isocaprylic acid quality; The glycol ether content is 2%～3%, mineral oil content is 17%～20%.
Embodiment 2 preparation isocaprylic acid calcium soaps
A certain amount of calcium oxide, glycol ether, mineral oil are stirred in the 270L reactor, be warming up to 70 ℃～80 ℃, add isocaprylic acid, behind reaction 1h～1.5h, carry out decompression dehydration, be cooled to 50 ℃～60 ℃, the flat panel filter machine leads to nitrogen filtering, promptly gets isocaprylic acid series metal soap; Isocaprylic acid: CaO=1: 0.9～1, glycol ether consumption be the isocaprylic acid quality 13%～16%, the mineral oil consumption is 60%～80% of isocaprylic acid quality.
Embodiment 3 composite isocaprylic acid series of heat stablizers
In reactor, dihydroxyphenyl propane is dissolved in phosphorous acid ester by proportioning, control 80-90 ℃, until its dissolving, add calcium iso-octoate metallic soap and isocaprylic acid zinc metallic soap then successively and carry out composite (1.5: 1～2: 1), epoxy soybean oil and mineral oil, stir constant temperature 1.5h～2h, be cooled to 50 ℃ of decompress filters, get light yellow transparent liquid, be isocaprylic acid series of heat stablizer.
The quality index of gained calcium iso-octoate zinc compound heat stabilizer is as shown in table 1.
Table 1 product quality indicator
Embodiment 4 preparation citric acid calcium soap or citric acid zinc soaps
By proportioning citric acid is dissolved in the distilled water.Add calcium oxide or zinc oxide under the normal temperature in batches, treat solid dissolving, 1h～2h is complete in reaction, and solution is filtered, and treats filtrate leaving standstill, and the adularescent material is separated out, filter, washing, oven dry, citric acid calcium soap or citric acid zinc soap; The citric acid consumption is 0.4～0.5mol/L, and calcium oxide or zinc oxide dosage are 0.1～0.2mol/L.
Embodiment 5 composite citric acid series of heat stablizers
In the four neck flasks of 250mL, dihydroxyphenyl propane is dissolved in phosphorous acid ester by proportioning, control 80-90 ℃, until its dissolving, add citrate of lime metallic soap and zinc citrate metallic soap then successively and carry out composite (1.5: 1～2: 1), epoxy soybean oil and mineral oil, stir constant temperature 1.5h～2h, be cooled to 50 ℃ of decompress filters, get light yellow transparent liquid, be citric acid series of heat stablizer.
About in the processed and applied of product of the present invention in polyvinyl chloride (PVC) RESINS to the thermostable effect of PVC, specifically investigate the quiet dynamic stability of stablizer, implementation method is as follows.
Test recipe:
PVC(M1000) 100g
DOP 28g
ESO 2g
Stablizer 2.5g
Dynamic thermal stability test: by pouring into after the above-mentioned prescription weighing in the mill (echo board X (S) K-160), roller speed ratio 1: 1353, preliminary roller speed 8.92m/min, 180 ℃ of roller temperature, film thickness 0.5mm observes roll banding phenomenon and film variable color time, as the index of product dynamic stability quality.
The static heat stability test: the transparent film that above-mentioned prescription is tried at the mill central roll is cut into measure-alike thin slice, put into electric heating drum crazy loft drier (101-2A), temperature is set 190 ℃, every 5min viewing film variable color situation, as the index of product static stability quality.
For investigating the stability of calcium iso-octoate Zn composite heat stabilizer product of the present invention, the product of having chosen the same price of ground manufacturer production such as Danyang, Yixing and Taiwan simultaneously compares test, the results are shown in Table 2.
Table 2
Through comparing, the thermostability of product of the present invention obviously is better than with the price product.Product of the present invention has been successfully applied in outlet ball for health and the film, has obtained good effect.
Product of the present invention has possessed following advantage:
1. no dust pollution;
2. the good heat stability of product obviously is better than the product with price;
3. product is put to death surviving animals and is carried out autopsy, knot through the method for Kunming mouse per os gavage It is as seen unusual that the fruit postmortem has no naked eyes, determines substantially nontoxic.
Claims (8)
1, a kind of liquid composite thermal stabilizer, it is characterized in that: the component of this thermo-stabilizer is counted metallic soap 35%-50%, phosphorous acid ester 10%-25%, dihydroxyphenyl propane 1%-2%, epoxy soybean oil 5%-10%, mineral oil 15%-30% with the quality percentage, by the composite liquid composite thermal stabilizer that makes of proportioning; The general structure of metallic soap is: (RCOO)
xMe; Wherein RCOO is isocaprylic acid root or citric acid series acid group, and Me is calcium, zinc, barium, potassium or rare earth.
2, liquid composite thermal stabilizer according to claim 1 is characterized in that: acid group is the isocaprylic acid root in the general structure of metallic soap
, be isocaprylic acid series composite thermal stabilizer by the composite products obtained therefrom of proportioning.
3, liquid composite thermal stabilizer according to claim 1 is characterized in that: acid group is the acid group that citric acid series forms in the general structure of metallic soap, is citric acid series of heat stablizer by the composite products obtained therefrom of proportioning.
4, the preparation method of the described liquid composite thermal stabilizer of a kind of claim 1 is characterized in that: preparation isocaprylic acid series composite thermal stabilizer:
(1) preparation metallic soap: reaction equation is:
MeO+RCOOH→(RCOO)
xMe+H
2O
RCOOH is an isocaprylic acid in the formula, and Me is calcium, zinc, barium, potassium or rare earth,
Isocaprylic acid, glycol ether, mineral oil are stirred, be warming up to 70 ℃～80 ℃, add metal oxide MeO, isocaprylic acid: the MeO mol ratio is 1: 0.9～1.1, react after 1～1.5 hour, carry out decompression dehydration, be cooled to 50 ℃～60 ℃, carry out filtration under diminished pressure, promptly get isocaprylic acid series metal soap;
(2) compound heat stabilizer: dihydroxyphenyl propane is dissolved in phosphorous acid ester by proportioning, control 80-90 ℃, until its dissolving, add two or more isocaprylic acid metallic soaps, epoxy soybean oil and mineral oil then successively, stirred constant temperature 1.5～2 hours, be cooled to 50 ℃ of decompress filters, get light yellow transparent liquid, be isocaprylic acid series composite thermal stabilizer.
5. the preparation method of liquid composite thermal stabilizer according to claim 4 is characterized in that:
Preparation isocaprylic acid zinc metallic soap: isocaprylic acid: ZnO=1: 1～1.1, glycol ether consumption be the isocaprylic acid quality 3%～5%, the mineral oil consumption is 20%～25% of isocaprylic acid quality;
Or preparation calcium iso-octoate metallic soap: isocaprylic acid: CaO=1: 0.9～1, glycol ether consumption be the isocaprylic acid quality 13%～16%, the mineral oil consumption is 60%～80% of isocaprylic acid quality.
6. the preparation method of liquid composite thermal stabilizer according to claim 4 is characterized in that:
The used isocaprylic acid metallic soap of compound heat stabilizer is two kinds on calcium iso-octoate and an isocaprylic acid zinc, and the amount ratio of calcium iso-octoate and isocaprylic acid zinc is 1.5～2: 1.
7. the preparation method of the described liquid composite thermal stabilizer of claim 1 is characterized in that: preparation citric acid series composite thermal stabilizer:
(1) preparation metallic soap:
Citric acid is dissolved in the distilled water, adds metal oxide MeO under the normal temperature in batches, treat solid dissolving, react 1～2 hour fully, solution is filtered, treat filtrate leaving standstill, the adularescent material is separated out, and filters, washing, oven dry, gets citric acid metal soap; The citric acid consumption is 0.4～0.5mol/L, and metal oxide MeO consumption is 0.1～0.2mol/L; Described metal oxide MeO is the oxide compound of calcium, zinc, barium, potassium or rare earth;
(2) compound heat stabilizer: in the four neck flasks of 250mL, dihydroxyphenyl propane is dissolved in phosphorous acid ester by proportioning, control 80-90 ℃, until its dissolving, add one or both citric acid metal soaps, epoxy soybean oil and mineral oil then successively, stir constant temperature 1.5h～2h, be cooled to 50 ℃ of decompress filters, get light yellow transparent liquid, be citric acid series composite thermal stabilizer.
8. the preparation method of liquid composite thermal stabilizer according to claim 7 is characterized in that:
The used metal oxide of preparation metallic soap is zinc oxide or calcium oxide, and the used citric acid metal of compound heat stabilizer soap is zinc citrate and/or citrate of lime.
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| CN101880407B (en) * | 2010-05-24 | 2013-06-12 | 陕西生益科技有限公司 | Method for preparing modified epoxy soybean oil for electronic grade product copper clad laminate |
| CN102516597B (en) * | 2011-12-13 | 2013-04-17 | 江南大学 | Special metal salt monomer for vegetable oil based liquid heat stabilizer and preparation method thereof |
| CN102532608B (en) * | 2011-12-15 | 2013-05-15 | 湖北犇星化工有限责任公司 | Heat stabilizer containing liquid barium and zinc, preparation method thereof and application thereof |
| CN102604268B (en) * | 2012-03-20 | 2013-08-21 | 江南大学 | Method for preparing environmentally-friendly PVC (polyvinyl chloride) magnesium-zinc liquid thermal stabilizer |
| CN103254524B (en) * | 2013-05-03 | 2015-12-02 | 重庆宝华化学助剂厂 | Nontoxic rare earth calcium zinc stabilizer and production method thereof |
| CN105111620B (en) * | 2015-09-10 | 2017-09-22 | 广州盈塑新材料科技有限公司 | A kind of Ye Ti Gai ∕ zinc heat stabilizers, its preparation method and the equipment for implementing this method |
| CN107602922A (en) * | 2017-08-07 | 2018-01-19 | 郑州庆宏塑胶科技有限公司 | A kind of preparation method of itaconic acid bright-coloured composite thermal stabilizer |
| CN110066522A (en) * | 2019-04-25 | 2019-07-30 | 安徽华文塑胶科技有限公司 | Anti- precipitation liquid stabilizer of one kind and preparation method thereof |
| CN111635305A (en) * | 2020-07-01 | 2020-09-08 | 中山华明泰科技股份有限公司 | Preparation method and application of composite zinc isooctanoate |
| CN113667190A (en) * | 2021-05-18 | 2021-11-19 | 广州城建职业学院 | Biodegradable modified starch-based toy material and preparation method of toy thereof |
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