CN107057113A - The method of in-situ modified terephthalic acid (TPA) aluminium - Google Patents
The method of in-situ modified terephthalic acid (TPA) aluminium Download PDFInfo
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- CN107057113A CN107057113A CN201710231733.XA CN201710231733A CN107057113A CN 107057113 A CN107057113 A CN 107057113A CN 201710231733 A CN201710231733 A CN 201710231733A CN 107057113 A CN107057113 A CN 107057113A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a kind of method of in-situ modified terephthalic acid (TPA) aluminium, concretely comprise the following steps：（1）The water of modifying agent or ethanol solution are added in terephthalic acid (TPA) sodium solution and form mixed liquor；（2）Aluminum soluble salt is dissolved as certain concentration in water；（3）By step（1）With（2）The material of preparation is added in supergravity reactor, and 30 ~ 60min of stirring reaction is further continued for after discharging；（4）By step（3）Obtained material produces modified terephthalic acid (TPA) aluminium finished product by filtering, washing, drying.This method is simple, easy, and prepared modified product particle diameter is small, pattern is uniform, the good dispersion and good with the compatibility of matrix in matrix material, while PVC thermal stabilities are lifted, also has a certain degree of improvement result to the mechanical property of product.
Description
Technical field
The invention belongs to Field of Fine Chemicals, it is related to a kind of Method in situ modification of terephthalic acid (TPA) aluminium.
Background technology
Heat stabilizer is polyvinyl chloride（PVC）The auxiliary material that must add in formula, is processing and was using to prevent or slow down PVC
Thermal decomposition in journey, its addition is usually the 4% ~ 8% of PVC amounts.Counted according to plastics association, country's PVC consumptions reach within 2015
To 28,500,000 tons, averagely calculated by 5%, stabilizer country annual requirement is at 1,400,000 tons or so.With wood moulding and other new materials
Develop rapidly, PVC demand is expected to break through 30,000,000 tons of high pointes in recent years, also increasingly acute along with the demand of stabilizer
Increase.
Stabilizer mainly divides three major types：Complex lead salt, composite calcium zinc and organotin.Concrete condition is as follows：1. complex lead salt
Because cost performance it is high the characteristics of, still have in 60% PVC product and add, but the heavy metal such as lead has toxicity to human body and environment, it is flourishing
Country has forbidden to use, and China starts legislation in limitation service stage at present, interior over the next several years to be also in mandatory phase；2.
Organic tin thermostable effect is good, but its is expensive, and has potential toxic to human central nervous, is closed extensively
Note；3. calcium/zinc composite heat stabilizer integrates the characteristics of cost performance placed in the middle, environmental protection because of it, it has also become what Study of Stabilizer developed must
Right trend.But the stablizing effect of home products is poor, less demanding down-stream enterprise can only be moved into, middle and high end client is substantially by moral
The overseas-funded enterprises such as state's bear board, France Kai meter Sen are monopolized.
The preparation method of the terephthalic acid (TPA) aluminium for PVC heat stabilizer is mentioned in the A of Chinese patent CN 104119220：
Para-phthalic sodium is dissolved in water with aluminum nitrate (aluminium chloride, aluminum sulfate, aluminium hydroxide), stirred at 20~180 DEG C
1~24h of reaction is mixed, then filters, wash, dry, terephthalic acid (TPA) aluminium finished product is prepared, and carry out answering for PVC heat stabilizer
With.
A kind of method of ultrasonic controllable terephthalic acid (TPA) al whisker is provided in Chinese patent CN104672076A：Soluble aluminum
Salt is added in para-phthalic sodium clear liquid, after 1~10min is reacted under 1000kHz high-frequency ultrasonic, then 200 kHz's
5~20min is reacted under ultrasonic wave, final sediment is filtered, and in 150 DEG C of dryings.
Terephthalic acid (TPA) aluminium is the part formed by two carboxyl deprotonations in terephthalic acid (TPA), with aluminium ion coordination type
Into complex.The presence of carboxyl oxygen atom, not only forms the strong and weak hydrogen bond not waited easily between solvent molecule, also makes coordination
Because different degrees of reunion occurs for intermolecular force between compound.What terephthalic acid (TPA) aluminium was participated in PVC is surface reaction,
Particle diameter is smaller, specific surface area is bigger, and thermostable effect is more obvious；But terephthalic acid (TPA) aluminium belongs to polar molecule, works as particle size
It is small to a certain extent when, it may occur that reunite, it is impossible to which full effect plays thermally-stabilised function, and the particle of big particle diameter can also influence
The mechanical property of PVC product.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of method of in-situ modified terephthalic acid (TPA) aluminium.
To achieve these goals, the present invention is achieved through the following technical solutions：The present invention's is a kind of in-situ modified to benzene
The method of aluminum diformate, comprises the following steps：
（1）The water of modifying agent or ethanol solution are added in terephthalic acid (TPA) sodium solution and form mixed liquor；
（2）Aluminum soluble salt is dissolved as certain concentration in water；
（3）By step（1）With（2）The material of preparation is added in supergravity reactor, be further continued for after discharging stirring reaction 30 ~
60min；
（4）By step（3）Obtained material produces modified terephthalic acid (TPA) aluminium finished product by filtering, washing, drying.
The modifying agent is C8~C18One or more in sodium soap, addition is is generated terephthalic acid (TPA) aluminium weight
The 0.5% ~ 5.0% of amount.
Further, modifying agent is preferably one kind or several in sodium laurate, odium stearate, sodium palmitate, natrium ricinoleicum
Kind.
The one kind of aluminum soluble salt in aluminium chloride or aluminum sulfate, concentration is any.
Further, aluminum soluble salt is preferably aluminium chloride, and concentration range is 25%-31.5%.
Beneficial effect：The present invention prepares a kind of in-situ modified terephthalic acid (TPA) aluminium by simple, easy method.
Modified terephthalic acid (TPA) aluminum shot footpath is small, pattern is uniform, the good dispersion and good with the compatibility of matrix in matrix material,
While PVC thermal stabilities are lifted, also there is a certain degree of improvement result to the mechanical property of product.
Brief description of the drawings
Fig. 1 is the XRD spectra of embodiment 1.
Fig. 2 schemes for the SEM of embodiment 1.
Fig. 3 schemes for the SEM of comparative example 2.
Fig. 4 is sweeping for the plane of disruption of compound obtained by after modification terephthalic acid (TPA) aluminium prepared by embodiment 1 is added in PVC
Retouch the photo that electron microscope amplifies 400 times.
Fig. 5 is the plane of disruption of gained compound after unmodified terephthalic acid (TPA) aluminium prepared by comparative example 1 is added in PVC
SEM amplifies 400 times of photo.
Embodiment
The present invention is further illustrated by the following examples.It should be understood that these embodiments are the explainations of the present invention
And citing, the scope of the present invention is not limited in any form.
Embodiment 1
A kind of method of in-situ modified terephthalic acid (TPA) aluminium of the present invention, comprises the following steps：
（1）The aqueous solution of odium stearate is added in terephthalic acid (TPA) sodium solution and forms mixed liquor；
（2）Aluminium chloride is configured to the aqueous solution that concentration is 25%；
（3）By step（1）With（2）The material of preparation is added in supergravity reactor, and the min of stirring reaction 30 is further continued for after discharging；
（4）By step（3）Obtained material produces modified terephthalic acid (TPA) aluminium finished product by filtering, washing, drying.
The addition of above-mentioned odium stearate by generation terephthalic acid (TPA) aluminium weight 0.5%.
Fig. 1 is the XRD spectra of product prepared by the present embodiment, is contrasted with standard x RD cards, and prepared product is to benzene two
Aluminium triformate.
Embodiment 2
A kind of method of in-situ modified terephthalic acid (TPA) aluminium of the present invention, comprises the following steps：
（1）The ethanol solution of sodium laurate is added in terephthalic acid (TPA) sodium solution and forms mixed liquor；
（2）Aluminium chloride is configured to the aqueous solution that concentration is 31.5%；
（3）By step（1）With（2）The material of preparation is added in supergravity reactor, and stirring reaction 60min is further continued for after discharging；
（4）By step（3）Obtained material produces modified terephthalic acid (TPA) aluminium finished product by filtering, washing, drying.
The addition of above-mentioned sodium laurate by generation terephthalic acid (TPA) aluminium weight 5.0%.
Embodiment 3
（1）The aqueous solution of sodium palmitate is added in terephthalic acid (TPA) sodium solution and forms mixed liquor；
（2）Aluminum sulfate is configured to the aqueous solution that concentration is 20%；
（3）By step（1）With（2）The material of preparation is added in supergravity reactor, and stirring reaction 45min is further continued for after discharging；
（4）By step（3）Obtained material produces modified terephthalic acid (TPA) aluminium finished product by filtering, washing, drying.
The addition of above-mentioned sodium palmitate by generation terephthalic acid (TPA) aluminium weight 2%.
Embodiment 4
（1）The aqueous solution of natrium ricinoleicum is added in terephthalic acid (TPA) sodium solution and forms mixed liquor；
（2）Aluminum sulfate is configured to the aqueous solution that concentration is 30%；
（3）By step（1）With（2）The material of preparation is added in supergravity reactor, and stirring reaction 35min is further continued for after discharging；
（4）By step（3）Obtained material produces modified terephthalic acid (TPA) aluminium finished product by filtering, washing, drying.
The addition of above-mentioned sodium palmitate by generation terephthalic acid (TPA) aluminium weight 1.5%.
Embodiment 5
（1）The aqueous solution of Sodium Caprylate is added in terephthalic acid (TPA) sodium solution and forms mixed liquor；
（2）Aluminium chloride is configured to the aqueous solution that concentration is 15%；
（3）By step（1）With（2）The material of preparation is added in supergravity reactor, and stirring reaction 50min is further continued for after discharging；
（4）By step（3）Obtained material produces modified terephthalic acid (TPA) aluminium finished product by filtering, washing, drying.
The addition of above-mentioned Sodium Caprylate by generation terephthalic acid (TPA) aluminium weight 3.5%.
Embodiment 6
（1）The aqueous solution of sodium stearate is added in terephthalic acid (TPA) sodium solution and forms mixed liquor；
（2）Aluminium chloride is configured to the aqueous solution that concentration is 20%；
（3）By step（1）With（2）The material of preparation is added in supergravity reactor, and stirring reaction 32min is further continued for after discharging；
（4）By step（3）Obtained material produces modified terephthalic acid (TPA) aluminium finished product by filtering, washing, drying.
The addition of above-mentioned sodium stearate by generation terephthalic acid (TPA) aluminium weight 4%.
Comparative example 1
The difference of comparative example 1 and embodiment 1 is：
In step（1）In, the aqueous solution of odium stearate is added not in terephthalic acid (TPA) sodium solution.
Comparative example 2
The difference of comparative example 2 and embodiment 1 is：
In step（3）In, by step（1）With（2）The material of preparation is added in common tank reactor, and stirring is further continued for after discharging
React 30 min.
Experiment 1
Terephthalic acid (TPA) aluminium obtained by embodiment 1, comparative example 1 and comparative example 2 is subjected to application performance test.
Formula used（It is shown in Table 1）For：PVC-5 100, stabilizer 4, stearic acid 0.2, processing aid 2, impact modifier
10th, calcium carbonate 20, wherein stabilizer are added to become kind.Embodiment 1, comparative example 1 and comparative example is respectively adopted in formula 1,2 and 3
Terephthalic acid (TPA) aluminium obtained by 2.After by formula, all raw materials are premixed in high mixer, kneaded in 185 DEG C of mills
Slice, then in vulcanizing press（Condition：At 185 DEG C, 5min, pressurization 5min, cooling 5min are first preheated）Upper tabletting, sample preparation,
Tested by national standard, gained performance data is shown in Table 2.
The test recipe of table 1
| Project | Formula 1 | Formula 2 | Formula 3 |
| PVC-5 | 100 | 100 | 100 |
| Stearic acid | 0.2 | 0.2 | 0.2 |
| Processing aid | 2 | 2 | 2 |
| Impact modifier | 10 | 10 | 10 |
| Calcium carbonate | 20 | 20 | 20 |
| Embodiment 1 prepares terephthalic acid (TPA) aluminium | 4 | — | — |
| Comparative example 1 prepares terephthalic acid (TPA) aluminium | — | 4 | — |
| Comparative example 2 prepares terephthalic acid (TPA) aluminium | — | — | 4 |
The performance data of table 2
| Project | Formula 1 | Formula 2 | Formula 3 |
| Tensile strength, MPa | 51.3 | 42.3 | 44.2 |
| Elongation, % | 105 | 92 | 95 |
| Bending strength, MPa | 71.3 | 64.5 | 66.7 |
| Bending modulus, MPa | 3745 | 3011 | 3230 |
| Notch impact strength, MPa | 15.2 | 12.4 | 13.6 |
| Low temperature notched impact strength (- 15 DEG C × 24h), MPa | 11.3 | 8.6 | 9.3 |
| Vicat softening point, DEG C | 83.2 | 81.3 | 82.1 |
| 200 DEG C of heat-stable times, min | 68 | 53 | 58 |
Relatively it can be seen that by the data of table 2：The fine grain that is prepared using supergravity reactor, easy disperse modified terephthaldehyde
Sour aluminium compared with unmodified or coarse grain footpath terephthalic acid (TPA) aluminium, can be obviously improved composite heat resistance and its
His mechanical property.
Fig. 2's and Fig. 3 relatively can be seen that：Thinner, modification evenly can be prepared to benzene using supergravity reactor
Aluminum diformate.
Fig. 4's and Fig. 5 relatively can be seen that：Terephthalic acid (TPA) aluminium after modified has more excellent in matrix material
Dispersiveness.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, the present invention
Claimed scope is by appended claims, specification and its equivalent thereof.
Claims (6)
1. a kind of method of in-situ modified terephthalic acid (TPA) aluminium, it is characterised in that comprise the following steps：
（1）The water of modifying agent or ethanol solution are added in terephthalic acid (TPA) sodium solution and form mixed liquor；
（2）Aluminum soluble salt is dissolved as certain concentration in water；
（3）By step（1）With（2）The material of preparation is added in supergravity reactor, be further continued for after discharging stirring reaction 30 ~
60min；
（4）By step（3）Obtained material produces modified terephthalic acid (TPA) aluminium finished product by filtering, washing, drying.
2. the method for in-situ modified terephthalic acid (TPA) aluminium as claimed in claim 1, it is characterised in that the modifying agent is C8~
C18One or more in sodium soap.
3. the method for in-situ modified terephthalic acid (TPA) aluminium as claimed in claim 1 or 2, it is characterised in that the modifying agent is excellent
Elect the one or more in sodium laurate, odium stearate, sodium palmitate, natrium ricinoleicum as.
4. the method for the in-situ modified terephthalic acid (TPA) aluminium as described in claim 1,2 or 3, it is characterised in that the modifying agent
Addition by generation terephthalic acid (TPA) aluminium weight 0.5% ~ 5.0%.
5. the method for in-situ modified terephthalic acid (TPA) aluminium as claimed in claim 1, it is characterised in that the aluminum soluble salt choosing
One kind from aluminium chloride or aluminum sulfate, concentration is any.
6. the method for in-situ modified terephthalic acid (TPA) aluminium as claimed in claim 1 or 2, it is characterised in that the soluble aluminum
Salt is preferably aluminium chloride, and concentration of aqueous solution scope is 25%-31.5%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254666A (en) * | 1991-01-30 | 1993-10-19 | Institut Francais Du Petrole | Process for production of alkaline or alkaline-earth metal terephthalate or of terephthalic acid, of high purity, from polyol polyterephthalate and in particular from waste of an ethylene gylcol polyterephthalate |
| JPH06211909A (en) * | 1993-01-20 | 1994-08-02 | Tosoh Corp | Production of vinyl chloride polymer, and composition comprising the same |
| CN102585295A (en) * | 2012-01-12 | 2012-07-18 | 江苏爱特恩高分子材料有限公司 | Hydrotalcite composite heat stabilizer and application thereof |
| CN104119220A (en) * | 2013-04-23 | 2014-10-29 | 陈祥迎 | Aluminium terephthalate PVC heat stabilizer and preparation method thereof |
| CN104672076A (en) * | 2015-03-10 | 2015-06-03 | 常州市博洋新材料科技有限公司 | Method for ultrasonically controlling terephthalic acid aluminum whisker |
-
2017
- 2017-04-11 CN CN201710231733.XA patent/CN107057113B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254666A (en) * | 1991-01-30 | 1993-10-19 | Institut Francais Du Petrole | Process for production of alkaline or alkaline-earth metal terephthalate or of terephthalic acid, of high purity, from polyol polyterephthalate and in particular from waste of an ethylene gylcol polyterephthalate |
| JPH06211909A (en) * | 1993-01-20 | 1994-08-02 | Tosoh Corp | Production of vinyl chloride polymer, and composition comprising the same |
| CN102585295A (en) * | 2012-01-12 | 2012-07-18 | 江苏爱特恩高分子材料有限公司 | Hydrotalcite composite heat stabilizer and application thereof |
| CN104119220A (en) * | 2013-04-23 | 2014-10-29 | 陈祥迎 | Aluminium terephthalate PVC heat stabilizer and preparation method thereof |
| CN104672076A (en) * | 2015-03-10 | 2015-06-03 | 常州市博洋新材料科技有限公司 | Method for ultrasonically controlling terephthalic acid aluminum whisker |
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