CN114956984A - Production method, product and application of hexahydrophthalic acid calcium hydrate with accurately controlled hydration number - Google Patents
Production method, product and application of hexahydrophthalic acid calcium hydrate with accurately controlled hydration number Download PDFInfo
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- 230000036571 hydration Effects 0.000 title claims abstract description 38
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- -1 hexahydrophthalic acid calcium hydrate Chemical compound 0.000 title claims description 39
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 72
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 72
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 72
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 238000003756 stirring Methods 0.000 claims abstract description 57
- 239000000376 reactant Substances 0.000 claims abstract description 50
- 239000011268 mixed slurry Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 33
- NVOATNPLTPMTDG-UHFFFAOYSA-L calcium cyclohexane-1,2-dicarboxylate hydrate Chemical compound C1CCC(C(C1)C(=O)[O-])C(=O)[O-].O.[Ca+2] NVOATNPLTPMTDG-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000004743 Polypropylene Substances 0.000 claims description 26
- 229920001155 polypropylene Polymers 0.000 claims description 26
- XXHCQZDUJDEPSX-UHFFFAOYSA-L calcium;cyclohexane-1,2-dicarboxylate Chemical group [Ca+2].[O-]C(=O)C1CCCCC1C([O-])=O XXHCQZDUJDEPSX-UHFFFAOYSA-L 0.000 claims description 18
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 150000004677 hydrates Chemical class 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 6
- 239000012467 final product Substances 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000010899 nucleation Methods 0.000 abstract description 11
- 230000006911 nucleation Effects 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 5
- RWBHVFCAOJQFOO-UHFFFAOYSA-N [Ca].C1(C=2C(C(=O)O1)=CC=CC2)=O Chemical compound [Ca].C1(C=2C(C(=O)O1)=CC=CC2)=O RWBHVFCAOJQFOO-UHFFFAOYSA-N 0.000 abstract 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 66
- 239000002667 nucleating agent Substances 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 15
- 230000008025 crystallization Effects 0.000 description 15
- 238000001816 cooling Methods 0.000 description 14
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 9
- 229920005629 polypropylene homopolymer Polymers 0.000 description 8
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- ZQNPDAVSHFGLIQ-UHFFFAOYSA-N calcium;hydrate Chemical compound O.[Ca] ZQNPDAVSHFGLIQ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004682 monohydrates Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002397 thermoplastic olefin Polymers 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- JVCQBGFGUZJNFZ-UHFFFAOYSA-L calcium;phthalate;hydrate Chemical compound O.[Ca+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O JVCQBGFGUZJNFZ-UHFFFAOYSA-L 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
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- 239000002516 radical scavenger Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/08—Saturated compounds having a carboxyl group bound to a six-membered ring
- C07C61/09—Completely hydrogenated benzenedicarboxylic 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
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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- Health & Medical Sciences (AREA)
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Abstract
The invention relates to a production method of calcium hexahydrophthalate hydrate with a hydration number accurately controlled, and the calcium hexahydrophthalate hydrate with the hydration number less than 1 and application thereof, wherein the production method comprises the following steps: s1, heating a preset amount of hexahydrophthalic anhydride to be molten; s2, adding a predetermined amount of calcium hydroxide, stirring, and uniformly mixing the calcium hydroxide and the calcium hydroxide to form mixed slurry; s3, slowly adding a predetermined amount of water into the mixed slurry under stirring, and continuously stirring until the mixture is uniformly mixed; s4, standing for reaction to form a complete reactant; s5, crushing the complete reactant to obtain a finished product PA6Ca & nH 2 O, wherein 0<n<1. Preferably, the finished product PA6Ca ·nH 2 In O, n is preferably greater than 0.3 and less than 0.8. The production method is simple in process and environment-friendly, the calcium phthalic anhydride containing crystal water produced by the method has stable nucleation inductivity on the thermoplastic polymer, and the polymer product shows good balanced shrinkage and lower warping property.
Description
Technical Field
The invention relates to an organic matter synthesis method, in particular to a method for accurately controlling a hydration number of calcium hexahydrophthalate hydrate, the hydration number controllable calcium hexahydrophthalate hydrate prepared by the method and application of the hydration number controllable calcium hexahydrophthalate hydrate.
Background
With the rapid development of the plastic industry, thermoplastic polymers have been widely used in various fields, and particularly, thermoplastic polypropylene has been widely used in various fields due to its excellent characteristics of good mechanical properties, relatively low density, no toxicity, good heat resistance, good corrosion resistance, and easy molding. However, the crystallization temperature of polypropylene is low, the crystallization speed is slow, and the rigidity and the heat resistance of the product can not meet the requirements of service performance in certain specific fields. Therefore, research on modification of such thermoplastic polyolefins has been developed for many years, for example, methods for improving performance are continuously explored by adding nucleating agents and other auxiliary materials for promoting uniform and rapid nucleation of polypropylene, it is mature at present to build heterogeneous crystal nuclei by adding the nucleating agents, so as to promote the polypropylene to directly grow on the surface of the nucleating agents in a crystallization manner, increase nucleation density and increase crystallization speed, and due to the small spherulite size of the heterogeneous crystal nuclei, the crystallization density and crystallization uniformity of the polymer product are effectively improved, so as to improve the mechanical properties, thermodynamic properties and optical properties of the product.
There are several nucleating agents available to improve polypropylene crystallization, more typically calcium hexahydrophthalate nucleating agents which are disclosed in china patent CN1525992A at the earliest 9.1.2004 to increase the rate of crystallization, specifically compounds and compositions containing specific metal salts (especially calcium salts) of hexahydrophthalic acid (HHPA) to provide highly desirable properties in thermoplastic articles. HHPA derivatives can be used as nucleating and/or clarifying agents for such thermoplastics, and are practical to manufacture and easy to process. Such compounds provide excellent crystallization temperature, stiffness and acid scavenger compatibility for the target polyolefin. Also, this compound shows very low hygroscopicity and thus excellent storage stability as a powdery or granular formulation. The publication specifically describes the preparation method of specific HHPA salt, in particular the water environment synthesis method of HHPA calcium salt. As the HHPA calcium salt is synthesized in water environment, the monohydrate of the HHPA calcium salt is obtained due to insufficient drying during production.
According to the research, the anhydrous HHPA calcium salt and the HHPA calcium salt monohydrate can improve the nucleation crystallization performance of the polypropylene, although the anhydrous HHPA calcium salt and the HHPA calcium salt monohydrate can greatly accelerate the nucleation crystallization of the polypropylene, improve the processing efficiency of polypropylene products and show excellent industrial application value. However, calcium hexahydrophthalate nucleating agents currently available on the market are generally anhydrous organic salts, and the anhydrous organic salts cause rapid crystallization of polypropylene at a higher temperature when in use, and the rapid crystallization rate often causes that polymer products cannot meet the performance indexes of balanced shrinkage and low warpage. The mixing of anhydrous HHPA calcium salt and HHPA calcium salt monohydrate is also proposed to improve the defect that polymer products cannot meet the performance indexes of balanced shrinkage and low warpage, but the mixing is performed after anhydrous HHPA calcium salt finished products and HHPA calcium salt monohydrate finished products are respectively prepared and are physically mixed, but the product after physical mixing has the defect of uneven mixing, and in addition, the anhydrous HHPA calcium salt and the HHPA calcium salt monohydrate have certain difference in nucleation performance of polypropylene, so the improvement effect is not ideal, and the requirements of extremely fine performance indexes are difficult to meet.
In view of the above technical problems, the present invention provides a solution that can effectively improve the above technical problems by studying the crystallization mechanism of the existing calcium hexahydrophthalate and the nucleation mechanism thereof in polyolefin and verifying through a series of experiments.
Disclosure of Invention
Aiming at the technical defects of the existing calcium hexahydrophthalate nucleating agent, the invention provides a calcium hexahydrophthalate hydrate product with the hydration number of less than 1, wherein in the preparation process, the hydration number of the calcium hexahydrophthalate hydrate product is accurately controlled by controlling preparation raw materials and preparation process conditions, and finally the hydrate product can effectively improve the equilibrium shrinkage rate and warping degree of a polymer product. The invention also aims to provide a production method of the calcium hexahydrophthalate hydrate, which has the technical advantages of simple process, environmental friendliness and the like, and the hydration number of the calcium hexahydrophthalate hydrate is accurately controlled.
The invention provides a production method of hexahydro calcium phthalate hydrate with accurately controlled hydration number, which comprises the following steps:
s1, heating a preset amount of hexahydrophthalic anhydride to be molten;
s2, adding a predetermined amount of calcium hydroxide, stirring, and uniformly mixing the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding a predetermined amount of water into the mixed slurry under stirring, and continuously stirring until the water is uniformly mixed;
s4, standing for reaction to form a complete reactant;
s5, crushing the complete reactant to obtain a finished product.
Preferably, the predetermined amount of water added in step S3 is 5 to 50 wt% of the predetermined amount of hexahydrophthalic anhydride; more preferably, the predetermined amount of water added in step S3 is 15% to 30% of the predetermined amount of hexahydrophthalic anhydride.
Preferably, in the step S3, the predetermined amount of water is slowly and uniformly added at a speed that the stirring reaction temperature of the mixed slurry is maintained between 120 and 160 ℃.
Preferably, the standing reaction is carried out until the reactants are naturally cooled, so as to achieve complete reaction.
Preferably, the finished product is calcium hexahydrophthalate n hydrate (hereinafter referred to as PA6 Ca. nH) 2 O) of which 0<n<1。
Further, the predetermined amount of water added in step S3 is 15% to 30% of the predetermined amount of hexahydrophthalic anhydride.
Preferably, the finished product is PA6Ca & nH 2 O, wherein 0.3<n<0.8。
Preferably, the method also comprises a step of detecting the hydration number of the crystal water in the finished product, and if the hydration number n of the crystal water in the finished product is detected to be more than 0.8, the crystal water is placed in an oven at 105-110 ℃ for drying until the hydration number n is more than 0.3 and less than 0.8.
Secondly, the invention provides a calcium hexahydrophthalate having a hydration number of less than 1, in particular in that it is obtained according to the above-mentioned production process and its finished product is PA6 Ca. nH 2 O, wherein 0<n<1。
Preferably, the finished product is PA6Ca & nH 2 O, wherein 0.3<n<0.8。
Finally, the invention also provides the specific use of calcium hexahydrophthalate having a hydration number of less than 1, in particular for modifying thermoplastic polymers.
Preferably, the thermoplastic polymer is a polyolefin.
Preferably, the polyolefin is polypropylene or polyethylene.
Compared with the prior art, the production method of the calcium hexahydrophthalate hydrate capable of accurately controlling the hydration number has the following beneficial effects:
(1) the inventor creatively abandons the traditional aqueous solution reaction environment, so that reactant hexahydrophthalic anhydride and calcium hydroxide are separated from the aqueous environment to react, and the hexahydrophthalic anhydride and calcium hydroxide directly react under the catalysis of water, and the synthetic hydrate product containing specific hydration number can be effectively and accurately synthesized by controlling the addition amount and the addition speed of catalytic water, and is directly chemically synthesized and is a single substance, thereby ensuring the consistency of the nucleation performance of the synthetic hydrate product on polyolefin.
(2) The inventor creatively controls the reaction temperature by controlling the water adding amount and speed and accurately controlling the water adding speed, so that reactants can react controllably under the catalysis of water, the control problem of the reaction speed and the product form is effectively balanced, and the consistency of the product form is ensured on the premise of not influencing the production efficiency.
(3) The inventor creatively controls the reaction temperature accurately, so that the water generation and water loss amount in the production process are kept in a controllable range, the hydration number of the product is accurately controlled on the basis of ensuring the full reaction of hexahydrophthalic anhydride and calcium hydroxide, and the process of reducing the calcium hexahydrophthalate crystal water by baking in the later period is avoided, so that the production process of the product is more energy-saving and environment-friendly, a large amount of production water is saved, and the energy waste problem of drying and removing the crystal water can be reduced.
Compared with the prior art, the hexahydrophthalic acid calcium hydrate with the hydration number less than 1 provided by the invention has the following beneficial effects:
the inventor creatively finds that the nucleating agent for directly synthesizing the calcium hexahydrophthalate hydrate with a specific hydration number is better than the nucleating agent formed by mixing anhydrous calcium hexahydrophthalate and calcium hexahydrophthalate monohydrate, in the aspects of improving the polypropylene nucleating effect, balancing shrinkage and low warpage.
The inventor creatively discovers that different nucleating agent crystal structures can be formed by accurately controlling the hydration number of the calcium hexahydrophthalate, the nucleating agent crystal structures have better dispersibility and dissolution efficiency in molten polypropylene, and the polypropylene products are endowed with good mechanical and optical properties while the polypropylene alpha nucleation is stably induced, and meanwhile, the equilibrium shrinkage rate of the polypropylene products is improved, and the warping is reduced.
Drawings
FIG. 1 is a polarization display sheet of homo-polypropylene not modified by any nucleating agent;
FIG. 2 is a polarization display sheet of homo-polypropylene modified by calcium hexahydrophthalate free of crystal water;
FIG. 3 is a polarization display sheet of homo-polypropylene modified by calcium hexahydrophthalate monohydrate;
FIG. 4 is PA6Ca & 0.21H produced using the process of the invention 2 A polarization display sheet of O-modified homo-polypropylene;
FIG. 5 is PA6Ca & 0.61H produced using the process of the invention 2 A polarization display sheet of O-modified homo-polypropylene;
FIG. 6 is PA6Ca & 0.82H produced using the process of the invention 2 The partial light display of the O-modified homo-polypropylene.
Detailed Description
The method for producing calcium hexahydrophthalate hydrate with precisely controlled hydration number provided by the present invention is further described below with reference to specific embodiments, and it should be noted that the technical solution and design principle of the present invention are only described in detail below with reference to the optimized technical solution.
Firstly, the method for producing the calcium hexahydrophthalate hydrate with the hydration number accurately controlled, which is provided by the invention, has no loss of generality and comprises the following steps:
s1, heating a preset amount of hexahydrophthalic anhydride to be molten;
s2, adding a predetermined amount of calcium hydroxide, stirring, and uniformly mixing the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding a predetermined amount of water into the mixed slurry under stirring, and continuously stirring until the water is uniformly mixed;
s4, standing for reaction to form a complete reactant;
s5, crushing the complete reactant to obtain a finished product.
And the proportion of the preset amount of the added water to the preset amount of the hexahydrophthalic anhydride is different, so that the finished product PA6Ca nH can be accurately controlled 2 The value of n in O, wherein the value of n can be any value between greater than zero and less than 1 according to the control. The combination of the nucleating agent performance of the finished product and the control of the reaction temperature is considered, and the PA6Ca nH finished product is preferred 2 In O, n has a value of more than 0.3 and less than 0.8. Preferably, the predetermined amount of water is added at a speed to keep the stirring reaction temperature of the mixed slurry at 110 to 180 ℃, and the reaction heat temperature of the standing reaction is controlled at 120 to 160 ℃. The method for measuring the hydration number of the crystal water adopts a general volatile weight method, and the method is measured by a synchronous differential thermal gravimetric analyzer TGA/DSC by adopting the following steps: 1. a clean and dry 70 mu alumina crucible is selected, 5mg of sample is weighed in a sample dish with known mass, and the sample is accurately weighed to 0.01mg in the sample dish. 2. And (3) placing the crucible containing the sample into a sample cell at 105 ℃, and stably introducing dry gas, Reactive gas: nitrogen, 50 mL/min; protective gas, nitrogen, 20mL/min gas purity greater than 99.99%, at this steady stateKeeping the temperature of the sample constant for about 5min until the weight of the sample is basically constant. 3. Then the temperature is programmed to rise to 300 ℃ at a speed of 10 ℃/min. And calculating the hydration number of the sample according to the loss amount of the crystal water of the sample in the temperature rising process.
The production method is further illustrated by specific experiments on the reaction ratio of hexahydrophthalic anhydride, calcium hydroxide and water and specific reaction parameter control.
Example 1
S1, heating 200g of hexahydrophthalic anhydride to 50 ℃ until the hexahydrophthalic anhydride is completely molten;
s2, adding 96.5g of calcium hydroxide, and stirring to uniformly mix the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding 5g of water into the mixed slurry of the hexahydrophthalic anhydride and the calcium hydroxide under stirring, wherein the amount of the water is 2.5 percent of that of the hexahydrophthalic anhydride, and continuously stirring until the mixture is uniformly mixed, wherein the reaction temperature is only about 100 ℃;
s4, standing for reaction, wherein the exothermic temperature of the reaction is about 104 ℃, and the reaction is slow until the reaction cannot be completed by natural cooling.
Example 2
S1, heating 200g of hexahydrophthalic anhydride to 50 ℃ until the hexahydrophthalic anhydride is completely molten;
s2, adding 96.5g of calcium hydroxide, and stirring to uniformly mix the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding 10g of water into the mixed slurry of the hexahydrophthalic anhydride and the calcium hydroxide under stirring, wherein the amount of the water is 5 percent of that of the hexahydrophthalic anhydride, and continuously stirring until the mixture is uniformly mixed, so that the reaction temperature is kept at about 180 ℃;
s4, standing for reaction, wherein the exothermic temperature of the reaction is about 186 ℃, and naturally cooling the reactant until the reactant is completely reacted to obtain a product;
s5, crushing the complete reactant to form PA6Ca & 0.1H 2 And (4) O, finishing the product.
Example 3
S1, heating 200g of hexahydrophthalic anhydride to 50 ℃ until the hexahydrophthalic anhydride is completely molten;
s2, adding 96.5g of calcium hydroxide, and stirring to uniformly mix the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding 15g of water into the mixed slurry of the hexahydrophthalic anhydride and the calcium hydroxide under stirring, wherein the amount of the water is 7.5 percent of that of the hexahydrophthalic anhydride, and continuously stirring until the mixture is uniformly mixed, so that the reaction temperature is kept at about 180 ℃;
s4, standing for reaction, wherein the exothermic temperature of the reaction is about 178 ℃, and naturally cooling the reactant until the reactant is completely reacted to obtain a product;
s5, crushing the complete reactant to form PA6Ca & 0.14H 2 And (4) O, finishing.
Example 4
S1, heating 200g of hexahydrophthalic anhydride to 50 ℃ until the hexahydrophthalic anhydride is completely molten;
s2, adding 96.5g of calcium hydroxide, and stirring to uniformly mix the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding 20g of water into the mixed slurry of the hexahydrophthalic anhydride and the calcium hydroxide under stirring, wherein the amount of the water is 10 percent of that of the hexahydrophthalic anhydride, and continuously stirring until the mixture is uniformly mixed, so that the reaction temperature is kept at about 170 ℃;
s4, standing for reaction, wherein the exothermic temperature of the reaction is about 172 ℃, and naturally cooling the reactant until the reactant is completely reacted to obtain a product;
s5, crushing the complete reactant to form PA6Ca & 0.21H 2 And (4) O, finishing.
Example 5
S1, heating 200g of hexahydrophthalic anhydride to 50 ℃ until the hexahydrophthalic anhydride is completely molten;
s2, adding 96.5g of calcium hydroxide, and stirring to uniformly mix the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding 25g of water into the mixed slurry of the hexahydrophthalic anhydride and the calcium hydroxide under stirring, wherein the amount of the water is 12.5 percent of that of the hexahydrophthalic anhydride, and continuously stirring until the mixture is uniformly mixed, so that the reaction temperature is kept at about 170 ℃;
s4, standing for reaction, wherein the exothermic temperature of the reaction is about 167 ℃, and naturally cooling the reactant until the reactant is completely reacted to obtain a product;
s5, crushing the complete reactant to form PA6Ca & 0.25H 2 And (4) O, finishing.
Example 6
S1, heating 200g of hexahydrophthalic anhydride to 50 ℃ until the hexahydrophthalic anhydride is completely molten;
s2, adding 96.5g of calcium hydroxide, and stirring to uniformly mix the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding 30g of water into the mixed slurry of the hexahydrophthalic anhydride and the calcium hydroxide under stirring, wherein the amount of the water is 15% of that of the hexahydrophthalic anhydride, and continuously stirring until the mixture is uniformly mixed, so that the reaction temperature is kept at about 160 ℃;
s4, standing for reaction, wherein the exothermic temperature of the reaction is about 162 ℃, and naturally cooling the reactant until the reactant is completely reacted to obtain a product;
s5, crushing the complete reactant to form PA6Ca & 0.31H 2 And (4) O, finishing the product.
Example 7
S1, heating 200g of hexahydrophthalic anhydride to 50 ℃ until the hexahydrophthalic anhydride is completely molten;
s2, adding 96.5g of calcium hydroxide, and stirring to uniformly mix the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding 35g of water into the mixed slurry of the hexahydrophthalic anhydride and the calcium hydroxide under stirring, wherein the amount of the water is 17.5 percent of that of the hexahydrophthalic anhydride, and continuously stirring until the mixture is uniformly mixed, so that the reaction temperature is kept at about 150 ℃;
s4, standing for reaction, wherein the exothermic temperature of the reaction is about 154 ℃, and naturally cooling the reactant until the reactant is completely reacted to obtain a product;
s5, crushing the complete reactant to form PA6Ca & 0.45H 2 And (4) O, finishing.
Example 8
S1, heating 200g of hexahydrophthalic anhydride to 50 ℃ until the hexahydrophthalic anhydride is completely molten;
s2, adding 96.5g of calcium hydroxide, and stirring to uniformly mix the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding 40g of water into the mixed slurry of the hexahydrophthalic anhydride and the calcium hydroxide under stirring, wherein the amount of the water is 20 percent of that of the hexahydrophthalic anhydride, and continuously stirring until the mixture is uniformly mixed, so that the reaction temperature is kept at about 140 ℃;
s4, standing for reaction, wherein the exothermic temperature of the reaction is about 143 ℃, and naturally cooling the reactant until the reactant completely reacts to obtain a product;
s5, crushing the complete reactant to form PA6Ca & 0.61H 2 And (4) O, finishing.
Example 9
S1, heating 200g of hexahydrophthalic anhydride to 50 ℃ until the hexahydrophthalic anhydride is completely molten;
s2, adding 96.5g of calcium hydroxide, and stirring to uniformly mix the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding 50g of water into the mixed slurry of the hexahydrophthalic anhydride and the calcium hydroxide under stirring, wherein the amount of the water is 25 percent of that of the hexahydrophthalic anhydride, and continuously stirring until the mixture is uniformly mixed, so that the reaction temperature is kept at about 130 ℃;
s4, standing for reaction, wherein the exothermic temperature of the reaction is about 134 ℃, and naturally cooling the reactant until the reactant is completely reacted to obtain a product;
s5, crushing the complete reactant to form PA6Ca & 0.65H 2 And (4) O, finishing.
Example 10
S1, heating 200g of hexahydrophthalic anhydride to 50 ℃ until the hexahydrophthalic anhydride is completely molten;
s2, adding 96.5g of calcium hydroxide, and stirring to uniformly mix the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding 60g of water into the mixed slurry of the hexahydrophthalic anhydride and the calcium hydroxide under stirring, wherein the amount of the water is 30 percent of that of the hexahydrophthalic anhydride, and continuously stirring until the mixture is uniformly mixed, so that the reaction temperature is kept at about 120 ℃;
s4, standing for reaction, wherein the exothermic temperature of the reaction is about 127 ℃, and naturally cooling the reactant until the reactant completely reacts to obtain a product;
s5, crushing the complete reactant to form PA6Ca & 0.76H 2 And (4) O, finishing.
Example 11
S1, heating 200g of hexahydrophthalic anhydride to 50 ℃ until the hexahydrophthalic anhydride is completely molten;
s2, adding 96.5g of calcium hydroxide, and stirring to uniformly mix the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding 70g of water into the mixed slurry of the hexahydrophthalic anhydride and the calcium hydroxide under stirring, wherein the amount of the water is 35 percent of that of the hexahydrophthalic anhydride, and continuously stirring until the mixture is uniformly mixed, so that the reaction temperature is kept at about 120 ℃;
s4, standing for reaction, wherein the exothermic temperature of the reaction is about 120 ℃, and naturally cooling the reactant until the reactant is completely reacted to obtain a product;
s5, crushing the complete reactant to form PA6Ca & 0.82H 2 And (4) O, finishing the product.
Example 12
S1, heating 200g of hexahydrophthalic anhydride to 50 ℃ until the hexahydrophthalic anhydride is completely molten;
s2, adding 96.5g of calcium hydroxide, and stirring to uniformly mix the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding 80g of water into the mixed slurry of the hexahydrophthalic anhydride and the calcium hydroxide under stirring, wherein the amount of the water is 40 percent of that of the hexahydrophthalic anhydride, and continuously stirring until the mixture is uniformly mixed, so that the reaction temperature is kept at about 110 ℃;
s4, standing for reaction, wherein the exothermic temperature of the reaction is about 110 ℃, and naturally cooling the reactant until the reactant is completely reacted to obtain a product;
s5, crushing the complete reactant to form PA6Ca & 0.91H 2 And (4) O, finishing.
Example 13
S1, heating 200g of hexahydrophthalic anhydride to 50 ℃ until the hexahydrophthalic anhydride is completely molten;
s2, adding 96.5g of calcium hydroxide, and stirring to uniformly mix the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding 100g of water into the mixed slurry of the hexahydrophthalic anhydride and the calcium hydroxide under stirring, wherein the amount of the water is 50 percent of that of the hexahydrophthalic anhydride, and continuously stirring until the mixture is uniformly mixed, so that the reaction temperature is kept at about 100 ℃;
s4, standing for reaction, wherein the exothermic temperature of the reaction is about 106 ℃, and naturally cooling the reactant until the reactant is completely reacted to obtain a product;
s5, crushing the complete reactant to form PA6Ca & 0.95H 2 And (4) O, finishing.
Example 14
S1, heating 200g of hexahydrophthalic anhydride to 50 ℃ until the hexahydrophthalic anhydride is completely molten;
s2, adding 96.5g of calcium hydroxide, and stirring to uniformly mix the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding 110g of water into the mixed slurry of the hexahydrophthalic anhydride and the calcium hydroxide under stirring, wherein the amount of the water is 55 percent of that of the hexahydrophthalic anhydride, and continuously stirring until the mixture is uniformly mixed, so that the reaction temperature is kept at about 100 ℃;
s4, standing for reaction, wherein the exothermic temperature of the reaction is about 102 ℃, and naturally cooling the reactant until the reactant is completely reacted to obtain a product;
s5, crushing the complete reactant to form PA6Ca & 1H 2 And (4) O, finishing.
When the water addition amount exceeds 40 percent of hexahydrophthalic anhydride, the reaction exothermic temperature is low, the standing reaction time is long, the crystalline hydration number of a product after complete reaction is more than 1, and when the crystalline hydration number is more than an expected value, the product needs to be placed in a drying oven at 105-110 ℃ for dehydration until the product is qualified.
To further verify the nucleation and modification properties of calcium hexahydrophthalate hydrate with a hydration number of less than 1 for thermoplastic polymers, comparative tests were carried out by the following experiments:
the PA6Ca and the monohydrate PA6Ca & 1H without crystal water 2 O and PA6 Ca. nH, the product obtained in experiments 2 to 14 2 Adding the O nucleating agent into a base material of homo-polypropylene (MI 17g/10min) according to the adding amount listed in the following table, uniformly mixing, extruding and molding sample bars, and placing the sample bars at a constant temperature of a constant temperature chamber of 23 DEG CTherefore, the performance test was performed after 48 hours. Respectively carrying out performance test analysis according to a haze test method GB/T2410-2008, a flexural modulus test method GB/T9341-2008 and a shrinkage and warpage test method GB/T17037.4-2003.
Wherein the warpage is 100% with a longitudinal shrinkage/transverse shrinkage ratio, the specific test results are as follows:
from the above table, it can be seen that the calcium hexahydrophthalate hydrate with the crystalline hydration number between 0 and 1 has unexpected advantages in improving the transparency, rigidity and warpage of the homopolypropylene over the non-crystalline water and the conventional monohydrate, especially the calcium hexahydrophthalate hydrate with the hydration number between 0.3 and 0.8 has obvious advantages in improving the above properties, and more especially shows the best improvement performance when the hydrate of calcium hexahydrophthalate is about 0.6. To further verify the nucleation superiority of calcium hexahydrophthalate hydrate with a hydration number of 0.6 as a single species, the polypropylene modification performance by precisely controlling the hydration number of calcium hexahydrophthalate hydrate was better than that of anhydrous calcium hexahydrophthalate, calcium hexahydrophthalate monohydrate and mixtures of both, as can be seen by comparing the data from comparative experiments 15, 16 and 17 with the data from 10, 7 and 5, respectively, in the above table, with the data from anhydrous calcium hexahydrophthalate and calcium hexahydrophthalate monohydrate mixed at approximately 2:8, 4:6, 7: 3.
To illustrate more visually the advantages of modification of thermoplastic polymers, in particular polypropylene, with calcium hexahydrophthalate hydrate of different hydration numbers produced according to the invention, PA6Ca & 0.21H obtained in the above experiment was used 2 O、PA6Ca·0.61H 2 O、PA6Ca·0.82H 2 O, and the comparative samples PA6Ca, PA6Ca & 1H 2 O, polarization microscopy was performed on a background sample without any nucleating agent. Specifically, the polypropylene melt is respectively melted with the homopolymerized polypropylene at 17g/10min in the dosage of 1000ppmPolypropylene pellets were produced under exponential conditions. The polypropylene particles were hot-melted and then formed into a film of about 20 μm by microscopic observation, and observed under a Leica DM2500P polarizing microscope at 500 times magnification, as shown in FIGS. 1 to 6, from the microscopic photographs, there was a clear difference in the size scale of the granular features, wherein the calcium hexahydrophthalate containing 0.21, 0.61, and 0.82 of the number of crystal hydrates gave small and uniform crystal sizes of the polypropylene, while the calcium hexahydrophthalate-modified polypropylene containing no crystal water and 1 crystal water had large and poor uniformity in the crystal sizes. From the above-mentioned microscopic view, it is further demonstrated that the calcium hexahydrophthalate hydrate containing specific hydrate produced by the method for producing calcium hexahydrophthalate hydrate with accurately controlled hydration number has better modification effect on thermoplastic polyolefin, especially polypropylene, and especially the calcium hexahydrophthalate hydrate is about 0.6 hydrate, so that the crystallization of the homopolymerized polypropylene is more uniform and the crystal is finer.
The foregoing is merely a preferred embodiment of the invention, and it is noted that the use of the terms "a" and "an" and "the" and similar referents herein is to be construed to cover both the singular and the plural, unless otherwise indicated; the terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms; recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, each separate value being incorporated into the specification as if it were individually recited herein; all methods described herein can be performed in any suitable order. The use of any and all examples, or exemplary language, provided herein is intended merely to better illuminate the subject matter of the application and does not pose a limitation on the scope of the subject matter unless otherwise claimed.
Preferred embodiments of the subject matter of this application, including the best mode known to the inventors for carrying out the claimed subject matter, are described herein, and should not be taken as limiting the invention, which is defined by the scope of the claims. Any variations which may be made by a person skilled in the art in light of the above description of preferred embodiments will be considered obvious by the detailed description herein. Therefore, it will be apparent to those skilled in the art that several step adjustments, simple technical substitutions, improvements and modifications can be made without departing from the spirit and scope of the invention, and these adjustments, substitutions, improvements and modifications should also be construed as the protection scope of the invention.
Claims (13)
1. A production method of calcium hexahydrophthalate hydrate with accurately controlled hydration number comprises the following steps:
s1, heating a preset amount of hexahydrophthalic anhydride to be molten;
s2, adding a predetermined amount of calcium hydroxide, stirring, and uniformly mixing the calcium hydroxide and the calcium hydroxide to form mixed slurry;
s3, slowly and uniformly adding a predetermined amount of water into the mixed slurry under stirring, and continuously stirring until the mixture is uniformly mixed;
s4, standing for reaction to form a complete reactant;
s5, crushing the complete reactant to obtain a finished product.
2. The method of claim 1, wherein the water is slowly and uniformly added in the step S3 at a predetermined rate to maintain the stirring reaction temperature of the mixed slurry at 120-160 ℃.
3. The method of claim 1, wherein the reaction is allowed to stand until the reaction mixture is naturally cooled to complete the reaction in step S4.
4. The method according to claim 1, wherein the predetermined amount of water added in step S3 is 5 to 50 wt% based on the predetermined amount of hexahydrophthalic anhydride.
5. The method of claim 4, wherein the predetermined amount of water added in step S3 is 15 to 30 wt% of the predetermined amount of hexahydrophthalic anhydride.
6. The method of claim 1, wherein the finished product is calcium hexahydrophthalate n-hydrate, where 0< n < 1.
7. The production process according to claim 6, wherein the finished product is calcium hexahydrophthalate n-hydrate, wherein 0.3< n < 0.8.
8. The production method according to any one of claims 4 to 7, further comprising a step of detecting the number of crystal water hydrates in the finished product, and if the number of crystal water hydrates n in the finished product is detected to be greater than 0.8, the finished product is dried in an oven at 105 to 110 ℃ until the number of crystal water hydrates n is greater than 0.3 and less than 0.8.
9. Calcium hexahydrophthalate hydrate with a hydration number less than 1, characterised in that it is obtained by the production process according to any one of claims 1 to 8, and the final product is calcium hexahydrophthalate n-hydrate, where 0< n < 1.
10. The calcium hexahydrophthalate hydrate of claim 9, wherein 0.3< n < 0.8.
11. Use of calcium hexahydrophthalate hydrate having a hydration number lower than 1 according to claim 9 for modifying thermoplastic polymers.
12. The use of claim 11, wherein the thermoplastic polymer is a polyolefin.
13. Use according to claim 12, wherein the polyolefin is polypropylene or polyethylene.
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