CN101168499B

CN101168499B - Synthesis method for aluminum carboxylate nucleater without acidic byproduct

Info

Publication number: CN101168499B
Application number: CN200610113991XA
Authority: CN
Inventors: 王小强; 李吉春; 董炳利; 田亮; 程中克; 苟文甲; 景媛媛; 王玫; 陈礼金
Original assignee: China Petroleum and Natural Gas Co Ltd
Current assignee: China Petroleum and Natural Gas Co Ltd
Priority date: 2006-10-24
Filing date: 2006-10-24
Publication date: 2011-05-25
Anticipated expiration: 2026-10-24
Also published as: CN101168499A

Abstract

The invention relates to a method for synthesizing an aluminum carboxylate salt nucleating agent without generating acid by-product, which is obtained by adding a neutralization reaction product of an aromatic carboxylic acid and a soluble hydroxide drop by drop into a soluble aluminum slat solution, and carrying out a displacement/hydroxylation reaction, limiting the OH<-> mol participated in the reaction and carried by hydroxide, which is 40-60% over than the -COOH participated in the reaction and carried by the aromatic carboxylic acid in the neutralization, in the displacement/hydroxylation reaction, the mol amount of the soluble aluminum salt Al<3+> being 45-55% of the aromatic carboxylic acid, ensuring the reaction process not to generate or generate the acid by-product as little as possible, and reducing the material demand on reactor in the reaction. The invention further enables not to generate the dihydroxy salt and non-hydroxy salt, or to generate the dihydroxy salt and non-hydroxy salt as little as possible, ensures the yield of target products of the mono-hydroxyl aromatic carboxylate aluminum salt, improves the purity of final product, and reduces the hardness and cost of following treatment.

Description

The ALUMINUM CARBOXYLIC salt nucleator synthetic method that a kind of no acidic by product generates

Technical field

The present invention relates to a kind of ALUMINUM CARBOXYLIC salt nucleator synthetic method, the ALUMINUM CARBOXYLIC salt nucleator synthetic method that particularly a kind of no acidic by product generates.Adopt this method can effectively reduce the growing amount of acidic by-products in the ALUMINUM CARBOXYLIC salt polyolefin nucleating agent building-up process, make two hydroxysalts and no hydroxy salt not generate or generation as few as possible, guarantee the growing amount of purpose product monohydroxy aromatic carboxylic acid aluminium salt, improve purity, reduction product difficulty of post-processing and the expense of final product, reduce requirement reactor material.

Background technology

Adopt the method for adding nucleator, improve polyolefine, bending particularly, tensile property are important channels of polypropylene being carried out enhancing modified.Aromatic carboxylic acid metallic soap class is that a class has the nucleator that increases firm and transparent modified effect to polypropylene, and succeeded in developing by SHELL company the sixties in 20th century, and Application and Development is morning, but modified effect is limited.

" research of the crosslinked PE of ALUMINUM CARBOXYLIC salt active filler reinforcement " (" polymer material science and engineering " in July, 1989 of woods pleasant virtue, Yu Qiang etc., the fourth phase) synthetic method that provides is that the product with organic carboxyl acid and sodium hydroxide neutralization reaction is added to Aluminum Chloride Hexahydrate (ALCl ₃6H ₂O) in the aqueous solution, replace/hydroxylating preparation aromatic carboxylic acid metallic soap class nucleator.Following two formulas of reaction formula:

General n is 1 or 2, and promptly the synthetic final product is monohydroxy salt, dihydroxyl salt, even does not have the mixture of hydroxy salt.Using this method can synthetic aroma family ALUMINUM CARBOXYLIC salt polyolefine enhancement nucleation agent, applied research is found: n=1, be synthetic product when being monohydroxy aromatic carboxylic acid aluminium salt, the enhancing modified effect obviously is better than the dihydroxyl aromatic carboxylic acid aluminium salt (n=2) and the aromatic carboxylic acid aluminium salt of hydroxyl not.But, though n=1 or n=2, according to above-mentioned reaction mole proportion relation, all can have hydrochloric acid to generate in the final product, reaction discharging waste liquid shows acid, contaminate environment, and reaction process is because the generation of acidic substance has proposed more harsh requirement to reactor material.When n=2, the reaction primary product is a dihydroxyl aromatic carboxylic acid aluminium salt in addition, and effect is not really desirable.

Summary of the invention

At the problems referred to above, in order to control and reduce the generation of acidic by-products in the reaction process, obtain with monohydroxy ALUMINUM CARBOXYLIC salt is the high purity aromatic carboxylic acids aluminium salt nucleator of benchmark, the contriver has carried out Related Experimental Study work, propose the ALUMINUM CARBOXYLIC salt nucleator synthetic method that a kind of no acidic by product generates, form the present invention.

Summary of the invention

For addressing the above problem, the invention provides the ALUMINUM CARBOXYLIC salt nucleator synthetic method that a kind of no acidic by product generates: the product of aromatic carboxylic acid and solubility oxyhydroxide neutralization reaction is added drop-wise in the soluble aluminum salt brine solution, replace/hydroxylating and obtaining, it is characterized in that in the first step neutralization reaction, reaction makes oxyhydroxide excessive, i.e. the OH of the oxyhydroxide participation reaction of carrying ^-The participation reaction of carrying with respect to aromatic carboxylic acid-molar weight (preferred 45%～55%) of COOH excessive 40%～60%; In the reaction of second step, oxyhydroxide carries excessive OH ^-The acidic substance that instant neutralization displacement/hydroxylating generates, in displacement/hydroxylating, soluble aluminum salt Al ³⁺Molar weight is aromatic monocarboxylate 45%～55% (preferred 48～52%).Temperature of reaction, reaction times can be used the used condition of prior art, and temperature of reaction is 45～60 ℃ usually, reaction times 1.0～2.0hr.In displacement/hydroxylating, soluble aluminum salt Al ³⁺Molar weight is aromatic monocarboxylate 45%～55%, can guarantee that like this two hydroxysalts and no hydroxy salt do not generate or generate as few as possible, thereby guaranteed the growing amount of purpose product monohydroxy aromatic carboxylic acid aluminium salt, improved final product purity, reduced product difficulty of post-processing and expense, reduced the acid of final relief liquor simultaneously and to the requirement of reactor material.

In synthetic reaction process, the first step neutralization reaction limits aromatic monocarboxylate, oxyhydroxide and aluminium salt molar ratio in specified range, the OH of the participation reaction that oxyhydroxide carries ^-The participation reaction of carrying with respect to the aromatic monocarboxylate-excessive 45%～55% (molar weight) of COOH, in the second step displacement/hydroxylating, soluble aluminum salt Al ³⁺Molar weight is the 45%～55% preferred 48～52% of aromatic monocarboxylate, and according to above-mentioned reaction feed proportioning, ALUMINUM CARBOXYLIC salt building-up reactions net reaction is as follows:

As seen,, in theory, do not generate acid on the reaction process macroscopic view, and the final purpose product is an effect ideal monohydroxy salt according to above-mentioned charging proportioning.Consider the different influence factor of the strong and weak degree of institute's soda acid that uses, the OH that the participation that recommendation oxyhydroxide carries is reacted ^-The participation reaction of carrying with respect to the aromatic monocarboxylate-excessive 40%～60% (molar weight) of COOH, preferred 45%～55%.Recommend soluble aluminum salt Al ³⁺Molar weight is aromatic monocarboxylate's 45～55%, preferred 48～52%.

The aromatic monocarboxylate can be selected from a kind of in phenylformic acid, n-butylbenzene formic acid, p t butylbenzoic acid, the toluylic acid etc. among the present invention.

Aluminum soluble salt can be selected from a kind of in aluminum chloride, aluminum nitrate, the Tai-Ace S 150 etc. among the present invention.

Effect of the present invention:

1. after testing, the pH value of the final relief liquor of building-up reactions is by original 4～5 or become about 7 than strong basicity, and acid-basicity reduces greatly.

2. synthetic nucleator only needs to remove the soluble salt that remains in the nucleator through water elution, and purity can reach more than 97%, does not need to remove two hydroxysalts and no hydroxy salt with other a large amount of organic solvents.

3. should synthetic nucleator of invention and the synthetic nucleator contrast of traditional method, be that PP tensile yield strength, bending property, heat-drawn wire increase rate are better than traditional method and synthesize nucleator under 0.3% the situation at addition.

4. should invention synthesize nucleator and the synthetic nucleator contrast of traditional method, the synthetic nucleator purity of this invention is higher than 5～14 percentage points of the synthetic nucleators of traditional method, and decomposition temperature exceeds 8～10 ℃.

The present invention limits aromatic carboxylic acid, oxyhydroxide and aluminium salt molar ratio in specified range by in synthetic reaction process, guarantees that reaction process does not generate or generate as few as possible acidic by-products, reduces the requirement of reaction process to reactor material.Make two hydroxysalts and no hydroxy salt not generate simultaneously or generation as few as possible, guarantee the growing amount of purpose product monohydroxy aromatic carboxylic acid aluminium salt, improve purity, reduction product difficulty of post-processing and the expense of final product.

Embodiment

Raw material sources and performance test methods:

PPF401: Lanzhou Petrochemical Company petroleum chemical plant

PP Vicat softening point: GB/T1633-2000

Tensile property: GB/1040-92

Flexural strength: GB9341-88

Embodiment 1

Get p t butylbenzoic acid 180.00g (1 mole), it is under agitation slowly added 61.30g (1.5 moles) the 30wt%NaOH aqueous solution, carry out neutralization reaction under 25 ℃, behind the reaction 30min, after reaction system presents the clarification homogeneous phase solution, with 125.25g (0.5 mole) 35wt%AlCl ₃6H ₂The O aqueous solution adds reaction system gradually, improves mixing speed, reacts 1.5hr under 55 ℃ of conditions, finishes reaction, filters, and collects filtrate, measures filtrate ph value; Water elution removes the soluble salt that remains in the nucleator, drying, and calculating with monohydroxy salt is the building-up reactions yield that calculates benchmark, the building-up reactions yield is an object of reference with the reactant p t butylbenzoic acid; The DSC method is measured decomposition temperature; Assay determination is the nucleator purity of calculating benchmark with monohydroxy salt.With nucleator PP is carried out the modification application test at last, measure modification situation PP Vicat softening point, tensile property, flexural strength.

Embodiment 2

Operation steps is with embodiment 1, and different is that the neutralization reaction temperature is 30 ℃, and reaction times 1.0hr, the consumption of NaOH are 57.21g (1.4 moles), and neutralization displacement/hydroxylating temperature is 45 ℃, reaction times 1.0hr.Assay determination and application test are with embodiment 1.

Embodiment 3

Operation steps is with embodiment 1, and neutralization reaction temperature that different is is for adding ℃, and reaction times 1.0hr, the consumption of NaOH are 65.39g (1.6 moles), and neutralization displacement/hydroxylating temperature is 60 ℃, reaction times 2.0hr.Assay determination and application test are with embodiment 1.

Embodiment 4

Get n-butylbenzene formic acid 180.00g (1 mole), it is under agitation slowly added 61.30g (1.5 moles) the 30wt%NaOH aqueous solution, carry out neutralization reaction under 30 ℃, behind the reaction 30min, after reaction system presents the clarification homogeneous phase solution, with 125.25g (0.5 mole) 35wt%AlCl ₃6H ₂The O aqueous solution adds reaction system gradually, improves mixing speed, reacts 1.5hr under 55 ℃ of conditions, finishes reaction, filters, and collects filtrate, measures filtrate ph value; Water elution removes the soluble salt that remains in the nucleator, drying, and calculating with monohydroxy salt is the building-up reactions yield that calculates benchmark, the building-up reactions yield is an object of reference with reactant n-butylbenzene formic acid; The DSC method is measured decomposition temperature; Assay determination is the nucleator purity of calculating benchmark with monohydroxy salt.With nucleator PP is carried out the modification application test at last, measure modification situation PP Vicat softening point, tensile property, flexural strength.

Embodiment 5

Operation steps is with embodiment 4, and different is that the neutralization reaction temperature is 25 ℃, reaction times 1.0hr, and displacement/hydroxylating uses AlCl ₃6H ₂O is 112.73g (0.45 mole), and temperature of reaction is 45 ℃, reaction times 2.0hr, and assay determination and application test are with embodiment 4.

Embodiment 6Operation steps is with embodiment 4, and different is that the neutralization reaction temperature is 25 ℃, reaction times 1.0hr, and displacement/hydroxylating uses AlCl ₃6H ₂O is 137.78g (0.55 mole), and temperature of reaction is 60 ℃, reaction times 2.0hr.Assay determination and application test are with embodiment 4.

Comparative Examples 1

Operation steps is with embodiment 1, and the consumption of NaOH is 53.12g (1.3 moles).Assay determination and application test are with embodiment 1.

Comparative Examples 2

Operation steps is with embodiment 1, and the consumption of NaOH is 69.47g (1.7 moles).Assay determination and application test are with embodiment 1.

Comparative Examples 3

Operation steps is with embodiment 4, and displacement/hydroxylating uses AlCl ₃6H ₂O is 100.20g (0.40 mole), and assay determination and application test are with embodiment 4.

Comparative Examples 4

Operation steps is with embodiment 4, and displacement/hydroxylating uses AlCl ₃6H ₂O is 150.31g (0.60 mole), and assay determination and application test are with embodiment 4.

The test-results of above embodiment and Comparative Examples is as shown in table 1 below.

Table 1

Claims

1. ALUMINUM CARBOXYLIC salt nucleator synthetic method that no acidic by product generates, the product of aromatic monocarboxylate and solubility oxyhydroxide neutralization reaction is added drop-wise in the soluble aluminum salt brine solution, replace/hydroxylating and obtaining, it is characterized in that in the first step neutralization reaction, reaction makes oxyhydroxide excessive, i.e. the OH of the oxyhydroxide participation reaction of carrying ^-The participation reaction of carrying with respect to the aromatic monocarboxylate-molar weight of COOH excessive 40%～60%; In the reaction of second step, oxyhydroxide carries excessive OH ^-The acidic substance that instant neutralization displacement/hydroxylating generates, in displacement/hydroxylating, soluble aluminum salt Al ³⁺Molar weight is aromatic monocarboxylate 45%～55%.

2. ALUMINUM CARBOXYLIC salt nucleator synthetic method according to claim 1 is characterized in that the OH of oxyhydroxide carries in the first step neutralization reaction participation reaction ^-The participation reaction of carrying with respect to the aromatic monocarboxylate-molar weight of COOH excessive 45%～55%.

3. ALUMINUM CARBOXYLIC salt nucleator synthetic method according to claim 1 is characterized in that in displacement/hydroxylating soluble aluminum salt Al ³⁺Molar weight is aromatic monocarboxylate 48～52%.

4. ALUMINUM CARBOXYLIC salt nucleator synthetic method according to claim 1 is characterized in that the aromatic monocarboxylate is selected from a kind of in phenylformic acid, n-butylbenzene formic acid, p t butylbenzoic acid, the toluylic acid.

5. ALUMINUM CARBOXYLIC salt nucleator synthetic method according to claim 1 is characterized in that aluminum soluble salt is selected from a kind of in aluminum chloride, aluminum nitrate, Tai-Ace S 150.

6. ALUMINUM CARBOXYLIC salt nucleator synthetic method according to claim 1 is characterized in that the neutralization reaction temperature is 25～30 ℃, reaction times 0.5～1.0hr.

7. ALUMINUM CARBOXYLIC salt nucleator synthetic method according to claim 1 is characterized in that in displacement/hydroxylating temperature of reaction is 45～60 ℃, reaction times 1.0～2.0hr.