CN106046606A - Maleamic acid-based calcium-zinc compound heat stabilizer as well as preparation method and application thereof - Google Patents
Maleamic acid-based calcium-zinc compound heat stabilizer as well as preparation method and application thereof Download PDFInfo
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- CN106046606A CN106046606A CN201610512755.9A CN201610512755A CN106046606A CN 106046606 A CN106046606 A CN 106046606A CN 201610512755 A CN201610512755 A CN 201610512755A CN 106046606 A CN106046606 A CN 106046606A
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- Prior art keywords
- ethylenediamine
- maleamic acid
- double
- heat stabilizer
- methanol solution
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- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 title claims abstract description 71
- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 11
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 title abstract 4
- 239000011701 zinc Substances 0.000 claims abstract description 59
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 ethanediamine maleic amide Chemical compound 0.000 claims abstract description 23
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 23
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 111
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 63
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 45
- 239000002131 composite material Substances 0.000 claims description 30
- 239000011575 calcium Substances 0.000 claims description 27
- 239000002585 base Substances 0.000 claims description 23
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000011592 zinc chloride Substances 0.000 claims description 9
- 235000005074 zinc chloride Nutrition 0.000 claims description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 8
- 239000001110 calcium chloride Substances 0.000 claims description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 125000003099 maleoyl group Chemical group C(\C=C/C(=O)*)(=O)* 0.000 claims 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 235000013539 calcium stearate Nutrition 0.000 claims 1
- 239000008116 calcium stearate Substances 0.000 claims 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 150000004291 polyenes Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a maleamic acid-based calcium-zinc compound heat stabilizer. The heat stabilizer is prepared from two different complexes represented by chemical formula [M(H2O)2L] through compounding, wherein M is selected from Ca or Zn, L represents an ethanediamine maleic amide acid radical, and n is selected from 1 or 2. According to the maleamic acid-based calcium-zinc compound heat stabilizer, the phenomenon of 'zinc burning' caused by taking a metal zinc heat stabilizer as a polyvinyl chloride heat stabilizer in the prior art is effectively improved, and the maleamic acid-based calcium-zinc compound heat stabilizer has good initial stainability resistance.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of double maleamic acid base Ca Zn composite thermally-stabilised
Agent and preparation method thereof, is that state natural sciences fund general project (approval number: 51173145) subsidizes achievement.
Background technology
Polrvinyl chloride Yin Qinai combustion, corrosion-resistant, cheap and transparent the advantage such as get well and extensively apply, but it is in the course of processing
In, there is the defect of poor heat stability, the self-catalyzed reaction of de-HCl easily occurs, forms conjugated polyene structure, cause its color to add
Deeply, mechanical properties decrease, therefore, the course of processing must be added heat stabilizer to suppress its thermal degradation.The most conventional PVC
Heat stabilizer is broadly divided into lead salts, metal soap, organic tin, terres rares, antimony organic class main stabilizer and organic auxiliary heat
Stabilizer.And all kinds of stabilizer is when being used alone, there is toxicity in various degree in lead salts, organic tin is the most on the high side.
At present, metal soap stabilizer is the second largest class main stabilizer that consumption is only second to lead salt, it is contemplated that environmental protection and nothing
The factors such as poison is inexpensive, add suppression of the preferable initial stage tinting efficiency of zinc salt, and calcium salt used time can delay again the phenomenons such as zinc burning,
So Ca Zn composite salt is the product that application is more.
Summary of the invention
The invention provides the double maleamic acid base Ca-Zn composite heat stabilizer of a kind of efficient ethylenediamine of environment-protecting asepsis and
Its preparation method, is used for overcoming existing heat stabilizer to contain heavy metal, complex process, expensive deficiency, and for mesh
The stability of front Ca-Zn composite heat stabilizer is not enough, prepares calcium Zn complex with the double maleamic acid of ethylenediamine for matrix, carries
For a kind of nontoxic, environmental protection, efficient, cheap novel polyvinyl-chloride use calcium/long-acting composite thermal stabilizer of zinc, alleviate due to
The interpolation of metallic zinc type thermal stabilizing agent and cause " zinc burning " phenomenon, there is good initial coloring.
Concrete, double maleamic acid base Ca-Zn composite heat stabilizers of present invention offer, by chemical formula [M (H2O)2L] institute
The two kinds of Different Complex shown are composited, wherein: M is the double maleamic acid root of ethylenediamine selected from Ca or Zn, L.
Preferably, shown in the structural formula such as formula (1) of the coordination compound shown in described chemical formula [M (H2O) 2L]:
Preferably, double maleamic acid base Ca-Zn composite heat stabilizers that the present invention provides are by chemical formula [Ca (H2O)2L] institute
The coordination compound shown and chemical formula [Zn (H2O)2L] shown in coordination compound be composited according to the ratio that mass ratio is 1-3:1-3.
It is highly preferred that by chemical formula [Ca (H2O)2L] shown in coordination compound and chemical formula [Zn (H2O)2L] shown in cooperation
Thing is composited according to the ratio that mass ratio is 2:3.
The preparation method of double maleamic acid base Ca-Zn composite heat stabilizers that the present invention provides, specifically includes following step
Rapid:
(1) with maleic anhydride as raw material, by maleic anhydride and ethylenediamine with the amount of material than the ratio as 2:1 respectively in second
Nitrile dissolves, under the conditions of ice-water bath, the acetonitrile solution of maleic anhydride is dropwise added drop-wise in the acetonitrile solution of ethylenediamine, fully stirs
After mixing reaction 3h, sucking filtration, after washing with alcohol three times, at 40 DEG C, evacuation is dried, and obtains the double maleamic acid of ethylenediamine, and reaction equation has
Shown in body such as formula (2)；
(2) alkali of the double maleamic acids of ethylenediamine and the amount of 2 times of materials is reacted in methanol solution, obtain ethylenediamine span
Carry out the methanol solution of amide hydrochlorate, the calcium chloride of the amount of the materials such as maleamic acid salt double with described ethylenediamine is dissolved in methanol
In, obtain the methanol solution of calcium chloride；Adjust the pH value of methanol solution of the double maleamic acid salt of ethylenediamine to 7-8, then to it dropwise
Dripping the methanol solution of described calcium chloride, 90-100 DEG C is stirred at reflux reaction, can obtain white precipitate, is dried product washing to perseverance
Weight, obtains the double maleamic acid calcium of ethylenediamine, and reaction equation is specifically as shown in formula (3)；
(3) alkali of the double maleamic acids of ethylenediamine and the amount of 2 times of materials is reacted in methanol solution, obtain ethylenediamine span
Carry out the methanol solution of amide hydrochlorate, the zinc chloride of the amount of the materials such as maleamic acid salt double with described ethylenediamine is dissolved in methanol
In, obtain the methanol solution of zinc chloride；Adjust the pH value of methanol solution of the double maleamic acid salt of ethylenediamine to 7-8, then to it dropwise
Dripping the methanol solution of described zinc chloride, 60-70 DEG C is stirred at reflux reaction, can obtain white precipitate, is dried product washing to perseverance
Weight, obtains the double maleamic acid zinc of ethylenediamine, and reaction equation is specifically as shown in formula (4)；
(4) under normal temperature and pressure, by double to ethylenediamine pair maleamic acid calcium and ethylenediamine maleamic acid zinc according to mass ratio
Ratio mix homogeneously for 1-3:1-3 i.e. prepares double maleamic acid base Ca-Zn composite heat stabilizer.
Double maleamic acid base Ca-Zn composite heat stabilizers that the present invention provides, as polychloroethylene heat stabilizer.
Present invention also offers a kind of polychloroethylene heat stabilizer, described polychloroethylene heat stabilizer includes that 0-75 part is stearic
Acid calcium, 0-12 part zinc stearate, 0-10 part beta-diketon, 0-10 part tetramethylolmethane, and 25-100 part any of the above-described described double
Maleic amide acidic group Ca-Zn composite heat stabilizer.
Preferably, the consumption of described polychloroethylene heat stabilizer is the 0.5-5% of polrvinyl chloride quality.
Double maleamic acid base Ca-Zn composite heat stabilizers that the present invention provides, effectively improve and use gold in prior art
Belong to zinc type thermal stabilizing agent, cause " zinc burning " phenomenon as polychloroethylene heat stabilizer, there is good anti-initial coloring.
Accompanying drawing explanation
The song of the heat-stable time of the calcium/zinc composite heat stabilizer of the different quality ratio that Fig. 1 provides for the embodiment of the present invention
Line chart；
The curve chart of single calcium/zinc heat stabilizer heat-stable time that Fig. 2 provides for the embodiment of the present invention.
Detailed description of the invention
In order to make those skilled in the art be more fully understood that, technical scheme can be practiced, below in conjunction with specifically
The invention will be further described for embodiment, but illustrated embodiment is not as a limitation of the invention.
Chemical reagent maleic anhydride used in following example of the present invention, ethylenediamine, acetonitrile, dehydrated alcohol, chlorination
Calcium, methanol, zinc chloride, octyl phthalate etc. all can commercially buy acquisition.
Embodiment 1
With maleic anhydride as raw material, by maleic anhydride and ethylenediamine with the amount of material than the ratio as 2:1 respectively at acetonitrile
Middle dissolving, under the conditions of ice-water bath, is dropwise added drop-wise to the acetonitrile solution of maleic anhydride in the acetonitrile solution of ethylenediamine, is sufficiently stirred for
After reaction 3h, sucking filtration, after absolute ethanol washing three times, at 40 DEG C, evacuation is dried.Obtain the double maleamic acid of ethylenediamine；
The sodium hydroxide of the double maleamic acids of ethylenediamine and the amount of 2 times of materials is reacted in methanol solution, obtains ethylenediamine
The methanol solution of double maleamic acid sodium, tune pH value to 7-8, then the methanol solution of calcium chloride, 100 DEG C of stirrings are dropwise dripped to it
Back flow reaction, can obtain white precipitate, is dried product washing to constant weight, obtains the double maleamic acid calcium of ethylenediamine；
The sodium hydroxide of the double maleamic acids of ethylenediamine and the amount of 2 times of materials is reacted in methanol solution, obtains ethylenediamine
The methanol solution of double maleamic acid sodium, tune pH value to 7-8, then the methanol solution of zinc chloride, 60 DEG C of stirrings are dropwise dripped to it
Back flow reaction, can obtain white precipitate, is dried product washing to constant weight, obtains the double maleamic acid zinc of ethylenediamine；
Under normal temperature and pressure, it is 1 by double to double for ethylenediamine maleamic acid calcium and ethylenediamine maleamic acid zinc according to mass ratio:
The ratio mix homogeneously of 1 i.e. prepares double maleamic acid base Ca-Zn composite heat stabilizer.
Embodiment 2
Concrete preparation method is identical with embodiment 1, and difference is only in that, the double maleamic acid calcium of ethylenediamine and second two
The double maleamic acid zinc of amine is combined according to the ratio that mass ratio is 1:2.
Embodiment 3
Concrete preparation method is identical with embodiment 1, and difference is only in that, the double maleamic acid calcium of ethylenediamine and second two
The double maleamic acid zinc of amine is combined according to the ratio that mass ratio is 1:3.
Embodiment 4
Concrete preparation method is identical with embodiment 1, and difference is only in that, the double maleamic acid calcium of ethylenediamine and second two
The double maleamic acid zinc of amine is combined according to the ratio that mass ratio is 2:1.
Embodiment 5
Concrete preparation method is identical with embodiment 1, and difference is only in that, the double maleamic acid calcium of ethylenediamine and second two
The double maleamic acid zinc of amine is combined according to the ratio that mass ratio is 2:3.
Embodiment 6
Concrete preparation method is identical with embodiment 1, and difference is only in that, the double maleamic acid calcium of ethylenediamine and second two
The double maleamic acid zinc of amine is combined according to the ratio that mass ratio is 3:1.
Embodiment 7
Double maleamic acid base Ca-Zn composite heat stabilizers obtained by embodiment 1-6 are as polychloroethylene heat stabilizer
Thermal stability evaluation during application.
(1) static heat stability test
First the double maleamic acid base Ca-Zn composite heat stabilizer 0.5-3 by PVC 100 parts, obtained by embodiment 1-6
Part, DOP (octyl phthalate) 80 parts, mix homogeneously, it is placed in baking oven, 120 DEG C of constant temperature 20min, prepare PVC test piece, then
Test piece is cut into the granular samples of 2mm × 2mm, according to GB/T2917.1-2002 congo red method: sample height in test tube is about
For 50mm, the bottom of Congored test paper is away from specimen surface about 25mm, and in 180 DEG C of constant temperature oil baths, record Congored test paper occurs
The significantly change blue time is the steady stability time.
(2) Dynamic Thermal stabilization time (roller examination method)
By the double maleamic acid base Ca-Zn composite heat stabilizers obtained by PVC and embodiment 1-6 according to certain ratio
After mix homogeneously, mixing on the rubber mixing machine of 170+3 DEG C, record sample starts time of blackening, is Dynamic Thermal stabilization time.
(3) baking the affected part after applying some drugs method experiment
With reference to ASTM2115-2004, PVC is tested print and be cut into the sheet specimens of 1cm × 1cm, be placed on aluminium-foil paper, put
Enter in the baking oven of 185 DEG C, observe color situation of change every 10min sampling.
Comparative example 1
With maleic anhydride as raw material, by maleic anhydride and ethylenediamine with the amount of material than the ratio as 2:1 respectively at acetonitrile
Middle dissolving, under the conditions of ice-water bath, is dropwise added drop-wise to the acetonitrile solution of maleic anhydride in the acetonitrile solution of ethylenediamine, is sufficiently stirred for
After reaction 3h, sucking filtration, after absolute ethanol washing three times, at 40 DEG C, evacuation is dried.Obtain the double maleamic acid of ethylenediamine；
The sodium hydroxide of the double maleamic acids of ethylenediamine and the amount of 2 times of materials is reacted in methanol solution, obtains ethylenediamine
The methanol solution of double maleamic acid sodium, tune pH value to 7-8, then the methanol solution of calcium chloride, 100 DEG C of stirrings are dropwise dripped to it
Back flow reaction, can obtain white precipitate, is dried product washing to constant weight, obtains the double maleamic acid calcium of ethylenediamine.
By double for ethylenediamine maleamic acid calcium separately as polychloroethylene heat stabilizer, carry out thermal stability evaluation, tool
The evaluation methodology of body is identical with the method for embodiment 7.
Comparative example 2
With maleic anhydride as raw material, by maleic anhydride and ethylenediamine with the amount of material than the ratio as 2:1 respectively at acetonitrile
Middle dissolving, under the conditions of ice-water bath, is dropwise added drop-wise to the acetonitrile solution of maleic anhydride in the acetonitrile solution of ethylenediamine, is sufficiently stirred for
After reaction 3h, sucking filtration, after absolute ethanol washing three times, at 40 DEG C, evacuation is dried.Obtain the double maleamic acid of ethylenediamine；
The sodium hydroxide of the double maleamic acids of ethylenediamine and the amount of 2 times of materials is reacted in methanol solution, obtains ethylenediamine
The methanol solution of double maleamic acid sodium, tune pH value to 7-8, then the methanol solution of zinc chloride, 60 DEG C of stirrings are dropwise dripped to it
Back flow reaction, can obtain white precipitate, is dried product washing to constant weight, obtains the double maleamic acid zinc of ethylenediamine.
By double for ethylenediamine maleamic acid zinc separately as polychloroethylene heat stabilizer, carry out thermal stability evaluation, tool
The evaluation methodology of body is identical with the method for embodiment 7.
As shown in Figure 1-2, the above results shows concrete outcome, and the heat-stable time of pure PVC is 2min, adds single second
After the double maleamic acid calcium of diamidogen or the double maleamic acid zinc heat stabilizer of ethylenediamine, heat-stable time respectively up to 15min and
11min.And when carrying out compounding by the two according to certain mass ratio, as Ca:Zn=2:3, thermostable effect is optimal, time thermally-stabilised
Between up to 36min.In oven aging experiments, can substantially observe, this kind of novel calcium/zinc composite heat stabilizer is to " zinc burning "
Phenomenon has clear improvement, and along with the increase of the double maleamic acid zinc amount of ethylenediamine, initial coloring is the best.
Above-mentioned evaluation test result shows: the heat-stable time of PVC is along with the double maleamic acid base Ca Zn composite of ethylenediamine
The increase of heat stabilizer consumption and increase, the initial stage heat stability of PVC has obtained progressively improving, and the ethylenediamine of general 2-3 part is double
Maleic amide acidic group Ca-Zn composite heat stabilizer can meet the thermally-stabilised needs to PVC.And the double maleamic acid of ethylenediamine
PVC initial coloring is significantly improved by base Ca-Zn composite heat stabilizer.
Embodiment described above is only the preferred embodiment lifted by absolutely proving the present invention, and its protection domain does not limits
In this.The equivalent that those skilled in the art are made on the basis of the present invention substitutes or conversion, all in the protection of the present invention
Within the scope of, protection scope of the present invention is as the criterion with claims.
Claims (8)
1. a double maleamic acid base Ca-Zn composite heat stabilizer, it is characterised in that by chemical formula [M (H2O)2L] shown in two
Plant Different Complex to be composited, wherein: M is the double maleamic acid root of ethylenediamine selected from Ca or Zn, L.
The most according to claim 1 pair of maleamic acid base Ca-Zn composite heat stabilizer, it is characterised in that described chemical formula
[M(H2O)2L] shown in coordination compound structural formula such as formula (1) shown in:
The most according to claim 1 and 2 pair of maleamic acid base Ca-Zn composite heat stabilizer, it is characterised in that by chemistry
Formula [Ca (H2O)2L] shown in coordination compound and chemical formula [Zn (H2O)2L] shown in coordination compound be 1-3:1-3's according to mass ratio
Ratio is composited.
The most according to claim 3 pair of maleamic acid base Ca-Zn composite heat stabilizer, it is characterised in that by chemical formula
[Ca(H2O)2L] shown in coordination compound and chemical formula [Zn (H2O)2L] shown in coordination compound multiple according to the ratio that mass ratio is 2:3
Conjunction forms.
The preparation method of the most according to claim 1 pair of maleamic acid base Ca-Zn composite heat stabilizer, it is characterised in that
Specifically include following steps:
(1) with maleic anhydride as raw material, by maleic anhydride and ethylenediamine with the amount of material than the ratio as 2:1 respectively in acetonitrile
Dissolve, under the conditions of ice-water bath, the acetonitrile solution of maleic anhydride is dropwise added drop-wise in the acetonitrile solution of ethylenediamine, be sufficiently stirred for anti-
After answering 3h, sucking filtration, after washing with alcohol three times, at 40 DEG C, evacuation is dried, and obtains the double maleamic acid of ethylenediamine；
(2) alkali of the double maleamic acids of ethylenediamine and the amount of 2 times of materials is reacted in methanol solution, obtain the double maleoyl of ethylenediamine
The methanol solution of amino acid salt, is dissolved in the calcium chloride of the amount of the materials such as maleamic acid salt double with described ethylenediamine in methanol,
Obtain the methanol solution of calcium chloride；The pH value of the methanol solution of the double maleamic acid salt of tune ethylenediamine is to 7-8, more dropwise drips to it
The methanol solution of described calcium chloride, 90-100 DEG C is stirred at reflux reaction, can obtain white precipitate, is dried product washing to constant weight,
Obtain the double maleamic acid calcium of ethylenediamine；
(3) alkali of the double maleamic acids of ethylenediamine and the amount of 2 times of materials is reacted in methanol solution, obtain the double maleoyl of ethylenediamine
The methanol solution of amino acid salt, is dissolved in the zinc chloride of the amount of the materials such as maleamic acid salt double with described ethylenediamine in methanol,
Obtain the methanol solution of zinc chloride；The pH value of the methanol solution of the double maleamic acid salt of tune ethylenediamine is to 7-8, more dropwise drips to it
The methanol solution of described zinc chloride, 60-70 DEG C is stirred at reflux reaction, can obtain white precipitate, is dried product washing to constant weight,
The double maleamic acid zinc of ethylenediamine；
(4), under normal temperature and pressure, it is 1-by double to double for ethylenediamine maleamic acid calcium and ethylenediamine maleamic acid zinc according to mass ratio
The ratio mix homogeneously of 3:1-3 i.e. prepares double maleamic acid base Ca-Zn composite heat stabilizer.
The most according to claim 1 pair of maleamic acid base Ca-Zn composite heat stabilizer, it is characterised in that as polychlorostyrene second
Alkene heat stabilizer.
7. a polychloroethylene heat stabilizer, it is characterised in that described polychloroethylene heat stabilizer includes 0-75 part calcium stearate,
0-12 part zinc stearate, 0-10 part beta-diketon, 0-10 part tetramethylolmethane, and described in 25-100 part any one of claim 1-4
Double maleamic acid base Ca-Zn composite heat stabilizers.
Polychloroethylene heat stabilizer the most according to claim 7, it is characterised in that the use of described polychloroethylene heat stabilizer
Amount is the 0.5-5% of polrvinyl chloride quality.
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| CN111592688A (en) * | 2020-05-28 | 2020-08-28 | 唐山师范学院 | Piperazine based amide acid salt heat stabilizer for PVC, preparation method thereof and PVC composite material |
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