CN101649069B - Plasticizing, oxidation resistance and thermal stabilization modifying agent of PVC material and preparation method thereof - Google Patents
Plasticizing, oxidation resistance and thermal stabilization modifying agent of PVC material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a plasticizing, oxidation resistance and thermal stabilization modifying agent of PVC material and a preparation method thereof, and the modifying agent is an organic compound. The preparation method comprises the following steps: 2-butine-1, 4-diol and 3,5-tert butyl-4-hydroxyphenyl propionic acid methyl ester carry out ester exchange reaction in an organic solvent under the action of an organic base catalyst to obtain 2-butine-, 4-diol dibasic acid (3,5- tert butyl-4-hydroxyphenyl propionic acid) esters; the 3,5- tert butyl-4-hydroxyphenyl propionic acid and a long-chain fatty acid carry out nucleophilic addition under the action of a cuprous salt catalyst to generate 2-fat acyloxy-2-butylene-1 and 4-diol dibasic acid (3,5-tert butyl-4-hydroxyphenyl propionic acid) esters. The main body of the compound is a triester which has the function of a plasticizer, and the 3,5- tert butyl-4-hydroxyphenyl propionic acid parts at two ends have the functions of catching free radicals and preventing PVC from being oxidized. Carbon-carbon double bond which is activated by acyloxy at the center is easy to carry out rapid addition with chlorine hydride, thereby preventing PVC from decomposing and changing color and playing the role of a heat stabilizer for PVC hot processing.
Description
Technical field
The present invention relates to a kind of plasticising of PVC material, anti-oxidant and thermal stabilization modifying agent; Belong to fine chemicals and compound method technical field thereof; Be specifically related to 2-fat acyloxy-2-butylene-1; Two (3,5-di-t-butyl-4-hydroxy phenylpropionic acid) ester cpds of 4-glycol and preparation method thereof, this compound is used for the plasticising of PVC material, anti-oxidant and thermally-stabilised modification.
Background technology
PVC is a kind of widely used macromolecular material.PVC must heat in the process of shaping makes it produce plasticity-, but in heat-processed, inevitably certain decomposition can take place, and mainly is that reaction takes place to eliminate, and generates carbon-carbon double bond and hydrogenchloride.If there is not stablizer to exist, the decomposition of the further catalysis PVC of hydrogenchloride meeting of generation produces the conjugated polyene structure, makes the product variable color, becomes fragile, and physical strength descends.Present commercial PVC thermo-stabilizer mainly contains: lead salts, metallic soap class and organic tin.Along with the reinforcement gradually of environmental consciousness, traditional plumbous type thermal stabilizing agent uses more and more to be restricted because serious contaminative is arranged.And organotin stabilizer and part metals soap class stablizer (outside deliming, magnesium, the aluminium soap) also have certain toxicity.In addition, the metallic soap one package stabilizer, like calcium-zinc composite stabilizing agent in the PVC hot-work later stage; When hydrogenchloride generates more for a long time; Fatty acid zinc can combine to produce zinc chloride with the hydrogenchloride of two molecules, and zinc chloride also is a kind of Lewis acid, can further decompose variable color by catalysis PVC conversely.Therefore, people are to nontoxic, and the increasing demand of the no metal fever stablizer of environmental protection is strong.The stablizer that design integrates multiple functions such as anti-oxidant, plasticising, fast light, anti-decompositions be following PVC stablizer develop main direction.
3,5-di-t-butyl-4 hydroxy phenylpropionic acid methyl esters is the oxidation inhibitor of using always, is that raw material also all is good oxidation inhibitor through exchanging the pentaerythritol tetrathioglycollate that obtains with tetramethylolmethane or glycol ester with two glycol esters with it.Their preparation mostly comes through transesterify under the alkaline condition, sees USP3644482.Carry out 3 under the tight bright aluminum isopropylate catalysis that proposes, the transesterification reaction of 5-di-t-butyl-4-hydroxy phenylpropionic acid methyl esters and isooctyl alcohol prepares 3, and the 5-di-t-butyl-different monooctyl ester of 4-hydroxy phenylpropionic acid is seen CN101168508A; Tight light also adopts the catalyzer of isocaprylic acid zinc as above-mentioned transesterify, sees CN101215235A, has obtained good result.
Relevant 2-butyne-1; The 4-glycol becomes the report of ester very many; Under acid catalysis, be dehydrated into the problem of ether easily in view of third alcoholic extract hydroxyl group of alkynes; Usually adopt the acyl chlorides of carboxylic acid in the presence of organic bases such as triethylamine, pyridine or mineral alkali, to accomplish, yet adopt chloride method to need a large amount of organic basess, aftertreatment is difficulty relatively.2-butyne-1,4-two is pure and mild 3, and 5-di-t-butyl-4-hydroxy phenylpropionic acid methyl esters all is the raw material that conveniently is easy to get, and their transesterification reaction is not appeared in the newspapers.In view of 2-butyne-1, the 4-glycol is to the susceptibility of protonic acid and Lewi s acid (being dehydrated into ether easily), and we attempt under basic catalyst catalysis, preparing 2-butyne-1 through transesterification reaction, two (3, the 5-di-t-butyl-4 hydroxy phenylpropionic acid) esters of 4-glycol.
The said 2-butyne that obtains-1; 4-glycol two (3; 5-di-t-butyl-4-hydroxy phenylpropionic acid) contains a carbon-carbon triple bond that nucleophilic addition takes place easily in the ester molecule, form the thiazolinyl ester bond, not only can have plastification if make itself and longer chain fatty acid carry out nucleophilic addition; Intermediary alkene ester functional group also has the ability of catching hydrogenchloride, can play the effect of PVC thermo-stabilizer.2-butyne-1 in the document (Chem.Lett 1981,641～644), 4-glycol diacetic acid esters and acetate, propionic acid, butyric acid and phenylformic acid carry out nucleophilic reaction under silver carbonate catalysis, and yield is 53～94%.Yet silver carbonate costs an arm and a leg, and certain toxicity is arranged.Document (J.Org.Chem.1989,54 (25): 5934～5938) 2-butyne-1 of having reported for work, 4-glycol diacetic acid esters under mercuric acetate catalysis with the nucleophilic addition of methyl alcohol.Yet organic mercury toxicity is bigger, has limited such Application of Catalyst.BASF AG uses venus crystals or venus crystals/copper powder to realize 2-butyne-1 as catalyzer in its patent (DE805760) respectively, 4-glycol diacetic acid esters, 2-butyne-1, and the nucleophilic addition of two benzylic ethers of 4-glycol and diacetyl oxide, but yield is on the low side.
Summary of the invention
For remedying the deficiency of prior art; The present invention provides a kind of plasticising of PVC material, anti-oxidant and thermal stabilization modifying agent; That is: 2-fat acyloxy-2-butylene-1; Two (3, the 5-di-t-butyl-4-hydroxy phenylpropionic acid) ester cpds of 4-glycol, this compound has good plasticising, anti-oxidant and thermally-stabilised function to the PVC material; Another object of the present invention provides the preparation method of this compound.
The plasticising of PVC material provided by the invention, anti-oxidant and thermal stabilization modifying agent, i.e. 2-fat acyloxy-2-butylene-1, two (3, the 5-di-t-butyl-4-hydroxy phenylpropionic acid) esters of 4-glycol, its general formula is following:
Wherein: R=CH
3(CH
2)
n-, n=6,8,10,12,14,16;
PVC material provided by the invention plasticising, anti-oxidant and thermal stabilization modifying agent, i.e. 2-fat acyloxy-2-butylene-1, the preparation method of two (3, the 5-di-t-butyl-4-hydroxy phenylpropionic acid) ester cpds of 4-glycol comprises the steps:
(1) preparation 2-butyne-1, two (3, the 5-di-t-butyl-4 hydroxy phenylpropionic acid) esters of 4-glycol
(1) with raw material 2-butyne-1,4-glycol, 3,5-di-t-butyl-ratio of 1: 2 in molar ratio of 4-hydroxy methyl propionate places the reactor drum that has separation column and prolong, adds organic alkali catalyst and organic solvent simultaneously;
(2) low-temperature heat, controlled temperature: 50～70 ℃, slowly refluxed 1 hour;
(3) improve temperature of reaction, 80～120 ℃ of temperature of reaction, the temperature of control fractionation capital is no more than 68 ℃, the reaction times: 1～20 hour;
(4) steam the methyl alcohol that generates stopped reaction when the amount of treating methyl alcohol reaches 20mL gradually;
(5) while hot reaction liquid is poured out reactor drum, cooling, suction filtration is isolated the solids of generation, seasoning.
(2) preparation 2-fat acyloxy-2-butylene-1, two (3, the 5-di-t-butyl-4-hydroxy phenylpropionic acid) esters of 4-glycol
(1), whipping device and reactor drum reflux condensing tube added the 2-butyne-1 for preparing in longer chain fatty acid and the step () in being arranged in 1: 1 in molar ratio; 4-glycol two (3; 5-di-t-butyl-4 hydroxy phenylpropionic acid) ester adds the cuprous salt catalyzer or contains the mixed catalyst of cuprous salt;
(2) be warmed up to 120～150 ℃, stirring reaction detects raw material point to TLC and disappears, and is cooled to 80 ℃;
(3) add hexanaphthene and reheat dissolving, filtered while hot, the white plates crystal is separated out in the filtrating cooling.
Said organic solvent is an acetonitrile, 1,4-dioxane or diethylene glycol dimethyl ether, and preferred solvent is an acetonitrile.Said organic alkali catalyst is a N-methyl-di-n-propylamine, 1,4-diazacyclo [2.2.2] octane, 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene or 1,5,7-three azabicyclics [4.4.0] last of the ten Heavenly stems-5-alkene.Preferred organic alkali catalyst is the N-methyl-di-n-propylamine.
Said longer chain fatty acid is n-caprylic acid, n-capric acid, positive laurostearic acid (LAURIC ACID 99 MIN), positive TETRADECONIC ACID (myristic acid), positive palmitic acid (Palmiticacid), n-octadecanoic acid (Triple Pressed Stearic Acid), suitable-9-octadecenoic acid (oleic acid), suitable; Suitable-9; 12-octadecadienoic acid (linolic acid) or suitable, suitable, suitable-9; 12,15-punicic acid (linolenic acid).The cuprous salt catalyzer is the sodium salt of cuprous acetate, the cuprous bromide longer chain fatty acid corresponding with selected longer chain fatty acid or the mixture of sylvite equimolar amount, or the sodium salt of the cuprous chloride longer chain fatty acid corresponding with selected longer chain fatty acid or the mixture of sylvite equimolar amount.Preferred cuprous salt catalyzer is a cuprous acetate.Preferred preparation 2-butyne-1, the temperature of reaction of two (3, the 5-di-t-butyl-4 hydroxy phenylpropionic acid) esters of 4-glycol is 82 ℃; Preparation 2-fat acyloxy-2-butylene-1, the temperature of reaction of two (3, the 5-di-t-butyl-4 hydroxy phenylpropionic acid) esters of 4-glycol is 130～140 ℃.
As everyone knows, monovalence silver ions and univalent copper ion can through with the complexing action activation acetylene bond of acetylene bond, therefore; Utilize cuprous salt to be catalyzer, explored 2-butyne-1,4-glycol two (3; 5-di-t-butyl-4-hydroxy phenylpropionic acid) nucleophilic addition of ester and lipid acid; And obtained 2-fat acyloxy-2-butylene-1 with the ideal yield, two (3, the 5-di-t-butyl-4 hydroxy phenylpropionic acid) esters of 4-glycol.The main body of this compound is one three ester, has the softening agent effect; 3 of two ends, 5-di-t-butyl-4 hydroxy phenyl partly has capturing free radicals, prevents PVC oxidized function in processing and use; Its center can be easily by acyloxy activatory carbon-carbon double bond and the rapid addition of the hydrogenchloride that produces in the PVC course of processing, prevents that PVC from further decomposing variable color, and the thermo-stabilizer effect is played in hot-work to PVC.The present invention utilizes cheap 2-butyne-1; 4-glycol, 3; 5-di-t-butyl-4-hydroxy phenylpropionic acid methyl esters and longer chain fatty acid be starting raw material, through transesterify and nucleophilic addition prepared one have plasticising, anti-oxidant and thermally-stabilised function roughly the same the time the PVC stablizer, i.e. 2-fat acyloxy-2-butylene-1; Two (3, the 5-di-t-butyl-4-hydroxy phenylpropionic acid) ester cpds of 4-glycol.Preparing method of the present invention is simple, and reaction conditions relaxes, and directly as the additive of the plasticising of PVC, anti-oxidant and thermally-stabilised function, method of use is simple for products obtained therefrom.
Embodiment
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1,
2-butyne-1, the preparation of two (3, the 5-di-t-butyl-4 hydroxy phenylpropionic acid) esters of 4-glycol
Put installation 500mL round-bottomed flask in the magnetic agitation electrically heated, wherein add 2-butyne-1,4-glycol 17.2g (0.2mol); Solvent 200mL, 3,5-di-t-butyl-4-hydroxy phenylpropionic acid methyl esters 117g (0.4mol); Catalyzer (0.01mol) is loaded onto and highly is the separation column of 60cm (interior glaze filler), at the fractionation capital still head and condenser west tube is installed; Transfer voltage, slowly reflux is 1 hour.Big a little then voltage, control fractionation column top temperature is no more than 68 ℃.Steam the methyl alcohol that generates stopped reaction when the amount of treating methyl alcohol reaches 20mL gradually.While hot reaction solution is poured out.The solid that cooling, suction filtration generate.Seasoning, weigh, calculate thick yield.Bullion till crystalline product is white, needle-shaped crystals, calculates crystallization yield with the acetonitrile recrystallization of equivalent.The result sees table 1, table 2.2-butyne-1, two (3, the 5-di-t-butyl-4-hydroxy phenylpropionic acid) esters of 4-glycol, fusing point: 132～134 ℃.
1H?NMR(500MHz，CDCl
3)：δ7.02(4H，s)，5.05(2H，s)，4.70(4H，s)，2.96(4H，t，J＝7.5Hz)，2.64(4H，t，J＝7.5Hz)，1.39(36H，s)。Ultimate analysis (C
38H
54O
6): measured value: C75.13, H8.99; Theoretical value: C75.21, H8.97.
Table 1 is that solvent slowly refluxes (82 ℃) result of different organic alkali catalyst catalyzed reactions with the acetonitrile
| Catalyzer | Reaction times/hour | Thick yield/% | The bullion color | Thick fusing point/℃ | Total recovery/% |
| Na 2CO 3 | 5.5 | 52 | Pale yellow | 122～128 | 41 (crystallizations 1 time) |
| K 2CO 3 | 5 | 56 | Pale yellow | 121～127 | 43 (crystallizations 1 time) |
| Sodium methylate | 8 | 44 | Palm fibre | 118～126 | 28 (crystallizations 2 times) |
| Pyridine | 10 | 36 | Reddish brown | 1115～125 | 19 (crystallizations 2 times) |
| The N-methyl-di-n-propylamine | 5 | 94 | White | 131～133 | 89 (crystallizations 1 time) |
| DABCO | 4 | 81 | Light color | 124～130 | 76 (crystallizations 1 time) |
| DBU | 4 | 82 | Light color | 123～131 | 76 (crystallizations 1 time) |
| TBD | 3 | 92 | White | 131～133 | 88 (crystallizations 1 time) |
[notes] DABCO:1,4-diazabicylo [2.2.2] octane; DBU:1,8-diazabicylo [5.4.0] 11 carbon-7-alkene; TBD:1,5,7-three azabicyclics [4.4.0] last of the ten Heavenly stems-5-alkene.
Table 2 is a catalyzer with the N-methyl-di-n-propylamine, the reaction result of different solvents
| Solvent | Reaction times/hour | Temperature of reaction/℃ | Thick yield/% | The result |
| Toluene | 15 | 105 | 0 | Do not react, it is pale brown that reaction solution becomes |
| Chlorobenzene | 15 | 110 | ＜5 | Product seldom, it is dark brown that reaction solution becomes |
| Acetonitrile | 5 | 82 | 94 | Crude product is a white |
| N, dinethylformamide | 5 | 110 | ＜5 | The reaction solution blackening, product is complicated, the difficult separation |
| DMSO 99.8MIN. | 5 | 110 | ＜5 | The reaction solution blackening, product is complicated, the difficult separation |
| 1, the 4-dioxane | 15 | 102 | 48 | Reaction solution becomes the dark brown light grey product of separating out |
| Diethylene glycol dimethyl ether | 15 | 110 | 52 | Reaction solution becomes the dark brown light grey product of separating out |
Above result shows that acetonitrile is optimal solvent, and the organic base catalytic effect is best, is that the solvent result is best with N-methyl-di-n-propylamine and TBD, considers that the TBD cost is higher, and selecting the N-methyl-di-n-propylamine for use is that solvent is optimum.
Embodiment 2
2-bay acyloxy-2-butylene-1, the preparation of two (3, the 5-di-t-butyl-4-hydroxy phenylpropionic acid) esters of 4-glycol.
One the 2-butyne-1 that adds process crystallization purifying among the embodiment 1 in the churned mechanically 500mL there-necked flask is housed; 4-glycol two (3; 5-di-t-butyl-4 hydroxy phenylpropionic acid) ester 60.7g (0.1mol), LAURIC ACID 99 MIN (positive laurostearic acid) 20.0g (0.1mol), catalyzer (0.002mol).Load onto reflux condensing tube, TM, be warmed up to certain temperature stirring reaction, detect raw material point up to TLC and disappear, be cooled to 80 ℃, add the 200mL hexanaphthene and reheat dissolving, filtered while hot, the white plates crystal is separated out in the filtrating cooling, and the result lists in table 3.2-bay acyloxy-2-butylene-1, two (3, the 5-di-t-butyl-4-hydroxy phenylpropionic acid) esters of 4-glycol, fusing point: 104～106 ℃.
1H?NMR(500MHz，CDCl
3)：δ6.95(4H，s)，5.56(2H，s)，5.26(1H，t，J＝6.5Hz)，5.12(2H，d，J＝6.5Hz)，5.00(2H，s)，2.96-2.85(4H，m)，2.65-2.50(6H，m)，1.52(2H，m)，1.35-1.20(52H，m)，0.93(3H，t，J＝7.5Hz)。Ultimate analysis (C
50H
78O
8): measured value: C74.29, H9.78; Theoretical value: C74.40, H9.94.
Table 3 LAURIC ACID 99 MIN nucleophilic addition condition optimizing test-results
| Catalyzer | Temperature of reaction/℃ | Reaction times/hour | Yield/% | The result |
| Sodium laurate | 140 | 10 | 0 | Do not react the reaction solution flavescence |
| Sodium laurate+CuCl | 125 | 8 | 84.4 | The reaction solution flavescence, product white |
| Sodium laurate+CuBr | 125 | 8 | 87.2 | The reaction solution flavescence, product white |
| Venus crystals | 140 | 10 | 0 | Do not react the reaction solution blackening |
| Verditer | 140 | 10 | 0 | Do not react the reaction solution blackening |
| Cuprous acetate | 120 | 10 | 90.3 | Reaction solution is pale yellow, product white |
| Cuprous acetate | 130 | 8 | 91.6 | The reaction solution flavescence, product white |
| Cuprous acetate | 140 | 6 | 89.1 | It is pale brown that reaction solution becomes, product white |
| Cuprous acetate | 150 | 4 | 86.9 | Reaction solution is deep yellow, product white |
By the visible cuprous salt of table 3 significant catalytic effect is arranged, wherein cuprous acetate is best, and temperature of reaction is controlled at 120～140 ℃ and is advisable.
Embodiment 3
2-palmitin acyloxy-2-butylene-1, the preparation of two (3, the 5-di-t-butyl-4-hydroxy phenylpropionic acid) esters of 4-glycol
One the 2-butyne-1 that adds process crystallization purifying among the embodiment 1 in the churned mechanically 500mL there-necked flask is housed; 4-glycol two (3; 5-di-t-butyl-4-hydroxy phenylpropionic acid) ester 60.7g (0.1mol), Palmiticacid (positive palmitic acid) 25.6g (0.1mol), cuprous acetate 0.245g (0.002mol).Dress changes goes up reflux condensing tube, TM, is warmed up to 135 ℃ of stirring reactions 11 hours, detects raw material point up to TLC and disappears; Be cooled to 80 ℃ of adding 200mL hexanaphthenes and reheat dissolving, filtered while hot, white plates crystal 80.3g is separated out in the filtrating cooling; Yield: 93.0%, fusing point: 97～99 ℃.
1H?NMR(500MHz，CDCl
3)：δ6.98(4H，s)，5.52(2H，s)，5.24(1H，t，J＝6.0Hz)，5.12(2H，d，J＝6.0Hz)，5.01(2H，s)，2.95-2.85(4H，m)，2.65-2.48(6H，m)，1.50(2H，m)，1.35-1.20(60H，m)，0.92(3H，t，J＝7.5Hz)。Ultimate analysis (C
54H
86O
8): measured value: C75.09, H10.06; Theoretical value: C75.13, H10.04.
Embodiment 4
2-stearyl acyloxy-2-butylene-1, the preparation of two (3, the 5-di-t-butyl-4 hydroxy phenylpropionic acid) esters of 4-glycol
One the 2-butyne-1 that adds process crystallization purifying among the embodiment 1 in the churned mechanically 500mL there-necked flask is housed; 4-glycol two (3; 5-di-t-butyl-4 hydroxy phenylpropionic acid) ester 60.7g (0.1mol), Triple Pressed Stearic Acid (n-octadecanoic acid) 28.5g (0.1mol), cuprous acetate 0.245g (0.002mol).Load onto reflux condensing tube, TM, be warmed up to 140 ℃ of stirring reactions 10.5 hours, detect raw material point up to TLC and disappear; Be cooled to 80 ℃ of adding 200mL hexanaphthenes and reheat dissolving; Filtered while hot, white plates crystal 77.9g, yield: 87.5% are separated out in the filtrating cooling.Fusing point: 92～93 ℃.
1H?NMR(500MHz，CDCl
3)：δ7.03(4H，s)，5.56(2H，s)，5.35(2H，m)，5.20(1H，t，J＝6.0Hz)，5.11(2H，d，J＝6.0Hz)，5.00(2H，s)，2.95-2.87(4H，m)，2.62-2.51(6H，m)，2.02(4H，m)，1.41-1.33(42H，m)，1.28-1.12(16H，m)，0.93(3H，t，J＝7.0Hz)。Ultimate analysis (C
56H
88O
8): measured value: C75.57, H10.02; Theoretical value: C75.63, H9.97.
Embodiment 5
2-oil acyloxy-2-butylene-1, the preparation of two (3, the 5-di-t-butyl-4 hydroxy phenylpropionic acid) esters of 4-glycol
One the 2-butyne-1 that adds process crystallization purifying among the embodiment 1 in the churned mechanically 500mL there-necked flask is housed, two (3,5-di-t-butyl-4 hydroxy phenylpropionic acid) the ester 60.7g (0.1mol) of 4-glycol; Oleic acid (suitable-the 9-octadecenoic acid) 28.3g (0.1mol), cuprous acetate 0.245g (0.002mol) loads onto reflux condensing tube, TM; Be warmed up to 125 ℃ of stirring reactions 12 hours; Detect raw material point up to TLC and disappear, be cooled to 80 ℃ of adding 200mL hexanaphthenes and reheat dissolving, filtered while hot; White plates crystal 77.9g, yield: 87.5% are separated out in the filtrating cooling.Fusing point: 92～93 ℃.
1H?NMR(500MHz，CDCl
3)：δ7.03(4H，s)，5.56(2H，s)，5.35(2H，m)，5.20(1H，t，J＝6.0Hz)，5.11(2H，d，.J＝6.0Hz)，5.00(2H，s)，2.95-2.87(4H，m)，2.62-2.51(6H，m)，2.02(4H，m)，1.41-1.33(42H，m)，1.28-1.12(16H，m)，0.93(3H，t，J＝7.0Hz)。Ultimate analysis (C
56H
88O
8): measured value: C75.57, H10.02; Theoretical value: C75.63, H9.97.
Embodiment 6
PT
Prescription: tested main body PVC is: SE (SG-5) powder 100g,
Additive is: product 20g among the embodiment 2～5; Contrast 1:DOP (phthalic acid two (2-ethylhexyl) ester) 20g; Contrast 2:DOP 20g, each 2g of calcium stearate and barium stearate.
Implementation method: polyvinyl chloride powder and thermo-stabilizer are mixed according to aforementioned proportion, put into beaker and under 150 ℃, carry out preplasticizing 20 minutes, and constantly stir, each composition is mixed.Compound is poured into clean and is preheating in 150 ℃ the screw extrusion press, extrude bean vermicelli shape sample.Choose sample test tensile strength and the elongation at break of length 10cm, get average value measured 3 times.Sample is shredded, accurately take by weighing and respectively organize sample 2.000g and be spread out in respectively in the clean petridish, put into and be preheating to 200 ℃ loft drier, at a distance from the glass port observation sample and write down time of flavescence, blackening respectively, heat and stopped in 2 hours heating.Watch-glass is taken out cool to room temperature, measure thermal weight loss, the result sees table 4.Test result shows: product of the present invention adds among the PVC, and its snappiness, tensile strength and elongation at break are compared ratio 1 and contrasted 2 and be significantly improved, and in addition, the oxidation-resistance and the thermotolerance of specimen also are significantly improved.
Table four, add among the embodiment PVC mechanical property and stability change behind the product
| Additive | Elongation at break/% | Tensile strength/MPa | Flavescence time/minute | Blackening time/minute | Color after 2 hours | Thermal weight loss/% |
| Contrast 1 | 214 | 48 | 15 | 32 | The pitch shape | 35.6 |
| Contrast 2 | 186 | 43 | 36 | 96 | Black | 15.4 |
| Product among the embodiment 2 | 228 | 56 | 105 | Strong yellow | 2.5 | |
| Product among the embodiment 3 | 247 | 58 | 102 | Pale yellow | 2.4 | |
| Product among the embodiment 4 | 251 | 63 | 98 | Pale yellow | 2.6 | |
| Product among the embodiment 5 | 262 | 59 | 85 | Pale brown | 3.5 |
Claims (8)
1. the plasticising of a PVC material, anti-oxidant and thermal stabilization modifying agent, that is: 2-fat acyloxy-2-butylene-1, two (3, the 5-di-t-butyl-4-hydroxy phenylpropionic acid) ester cpds of 4-glycol, its general formula is following:
Wherein:
R＝CH
3(CH
2)
n-，n＝6，8，10，12，14，16；
2. the preparation method of the plasticising of the said PVC material of claim 1, anti-oxidant and thermal stabilization modifying agent comprises the steps:
(1) preparation 2-butyne-1, two (3, the 5-di-t-butyl-4-hydroxy phenylpropionic acid) esters of 4-glycol
(1) with raw material 2-butyne-1,4-glycol, 3,5-di-t-butyl-ratio of 1: 2 in molar ratio of 4-hydroxy phenylpropionic acid methyl esters places the reactor drum that has separation column and prolong, adds organic alkali catalyst and organic solvent simultaneously;
(2) low-temperature heat, controlled temperature: 50～70 ℃, slowly refluxed 1 hour;
(3) improve temperature of reaction, 80～120 ℃ of temperature of reaction, the temperature of control fractionation capital is no more than 68 ℃, the reaction times: 1～20 hour;
(4) steam stopped reaction when methyl alcohol to be no longer included distillates to the methyl alcohol that generates gradually;
(5) while hot reaction liquid is poured out reactor drum, cooling, suction filtration is isolated the solids of generation, seasoning;
(2) preparation 2-fat acyloxy-2-butylene-1, two (3, the 5-di-t-butyl-4-hydroxy phenylpropionic acid) esters of 4-glycol
(1) in the reactor drum that whipping device and reflux condensing tube are arranged, added the 2-butyne-1 for preparing in longer chain fatty acid and the step () in 1: 1 in molar ratio; 4-glycol two (3; 5-di-t-butyl-4-hydroxy phenylpropionic acid) ester adds the cuprous salt catalyzer or contains the mixed catalyst of cuprous salt;
(2) be warmed up to 120～150 ℃, stirring reaction detects raw material point to TLC and disappears, and is cooled to 80 ℃;
(3) add hexanaphthene and reheat dissolving, filtered while hot, the white plates crystal is separated out in the filtrating cooling.
3. according to the preparation method of the plasticising of the said PVC material of claim 2, anti-oxidant and thermal stabilization modifying agent, it is characterized in that: said organic solvent is an acetonitrile, 1,4-dioxane or diethylene glycol dimethyl ether; Said organic alkali catalyst is a N-methyl-di-n-propylamine, 1,4-diazacyclo [2.2.2] octane, 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene or 1,5,7-three azabicyclics [4.4.0] last of the ten Heavenly stems-5-alkene.
4. according to the preparation method of the plasticising of claim 2 or 3 said PVC materials, anti-oxidant and thermal stabilization modifying agent, it is characterized in that: said organic alkali catalyst is the N-methyl-di-n-propylamine, and said organic solvent is an acetonitrile.
5. according to the preparation method of the plasticising of the said PVC material of claim 2, anti-oxidant and thermal stabilization modifying agent; It is characterized in that: said longer chain fatty acid is n-caprylic acid, n-capric acid, positive laurostearic acid, positive TETRADECONIC ACID, positive palmitic acid, n-octadecanoic acid, suitable-9-octadecenoic acid, suitable, suitable-9,12 octadecadienoic acid or suitable; Suitable; Suitable-9,12,15 punicic acids.
6. according to the preparation method of the plasticising of the said PVC material of claim 2, anti-oxidant and thermal stabilization modifying agent, it is characterized in that: said cuprous salt catalyzer is the sodium salt of the corresponding longer chain fatty acid of mixture or cuprous chloride and the selected longer chain fatty acid of sodium salt or sylvite equimolar amount of cuprous acetate, the cuprous bromide longer chain fatty acid corresponding with selected longer chain fatty acid or the mixture of sylvite equimolar amount.
7. according to the preparation method of the plasticising of claim 2 or 6 each said PVC materials, anti-oxidant and thermal stabilization modifying agent, it is characterized in that: said cuprous salt catalyzer is a cuprous acetate.
8. according to the preparation method of the plasticising of the said PVC material of claim 2, anti-oxidant and thermal stabilization modifying agent, it is characterized in that: said preparation 2-butyne-1, the temperature of reaction of two (3, the 5-di-t-butyl-4-hydroxy phenylpropionic acid) esters of 4-glycol is 82 ℃; Said preparation 2-fat acyloxy-2-butylene-1, the temperature of reaction of two (3, the 5-di-t-butyl-4-hydroxy phenylpropionic acid) esters of 4-glycol is 130～140 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644482A (en) * | 1961-10-30 | 1972-02-22 | Geigy Ag J R | (4-hydroxy-5-alkylphenyl) alkanoic acid esters of polyols |
| US3723503A (en) * | 1971-07-01 | 1973-03-27 | Ciba Geigy Corp | 3,5-dialkyl-4-hydroxyphenylalkanoic acid esters of 3-hydroxy-2,2-dimethylpropyl 3-hydroxy-2,2-dimethylpropionate |
| US3839278A (en) * | 1971-07-01 | 1974-10-01 | Ciba Geigy Corp | 3,5-dialkyl-4-hydroxyphenylalkanoic acid esters antioxidants |
| CN101168508A (en) * | 2007-06-07 | 2008-04-30 | 上海金海雅宝精细化工有限公司 | Method for preparing liquid hindered phenol antioxidants |
| CN101215235A (en) * | 2007-12-27 | 2008-07-09 | 上海金海雅宝精细化工有限公司 | Method for synthesizing hindered phenol antioxidants |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644482A (en) * | 1961-10-30 | 1972-02-22 | Geigy Ag J R | (4-hydroxy-5-alkylphenyl) alkanoic acid esters of polyols |
| US3723503A (en) * | 1971-07-01 | 1973-03-27 | Ciba Geigy Corp | 3,5-dialkyl-4-hydroxyphenylalkanoic acid esters of 3-hydroxy-2,2-dimethylpropyl 3-hydroxy-2,2-dimethylpropionate |
| US3839278A (en) * | 1971-07-01 | 1974-10-01 | Ciba Geigy Corp | 3,5-dialkyl-4-hydroxyphenylalkanoic acid esters antioxidants |
| CN101168508A (en) * | 2007-06-07 | 2008-04-30 | 上海金海雅宝精细化工有限公司 | Method for preparing liquid hindered phenol antioxidants |
| CN101215235A (en) * | 2007-12-27 | 2008-07-09 | 上海金海雅宝精细化工有限公司 | Method for synthesizing hindered phenol antioxidants |
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