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，CDCl₃)：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 (C₃₈H₅₄O₆): 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/%
						Na₂CO₃	5.5	52	Pale yellow	122～128	41 (crystallizations 1 time)
K₂CO₃	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，CDCl₃)：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 (C₅₀H₇₈O₈): 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，CDCl₃)：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 (C₅₄H₈₆O₈): 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，CDCl₃)：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 (C₅₆H₈₈O₈): 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，CDCl₃)：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 (C₅₆H₈₈O₈): 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

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＝CH₃(CH₂)_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;

(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;

(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;

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 ℃.