CN106831590A - A kind of 2 methylimidazole zinc salts and its preparation method and application - Google Patents
A kind of 2 methylimidazole zinc salts and its preparation method and application Download PDFInfo
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- CN106831590A CN106831590A CN201710025714.1A CN201710025714A CN106831590A CN 106831590 A CN106831590 A CN 106831590A CN 201710025714 A CN201710025714 A CN 201710025714A CN 106831590 A CN106831590 A CN 106831590A
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- methylimidazole
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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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
- C08K5/0091—Complexes with metal-heteroatom-bonds
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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
Abstract
A kind of 2 methylimidazole zinc salts and its preparation method and application, with zinc nitrate hexahydrate and 2 methylimidazoles as raw material, under catalyst action, obtain 2 methylimidazole zinc salts (ZIF 8)；2 methylimidazole zinc salts and calcium stearate, zinc stearate are compounded, Ca-Zn composite heat stabilizer is obtained.2 methylimidazole zinc salt heat stabilizers prepared by the present invention have the features such as big nontoxic, heavy metal free, specific surface area, environmental protection, made Ca-Zn composite heat stabilizer is a kind of efficient composite thermal stabilizer,, easy dispersion good with PVC compatibilities, while assigning PVC product more preferable initial stage and long-term thermal stability, the transparency.The preparation technology route is simple and environmentally-friendly, and raw material sources are abundant and cheap.
Description
Technical field
The invention belongs to plastic additive field, and in particular to a kind of 2-methylimidazole zinc salt and preparation method thereof and should
With.
Background technology
There are many defect sturctures in polyvinyl chloride (PVC) molecular structure, dechlorination easily occurs when heat, light, oxygen
Change hydrogen and degrade.With deepening constantly for palliating degradation degree, the color of polyvinyl chloride resin is constantly deepened, until close to black, and product
Mechanical property also be subject to heavy damage.Therefore need to add heat stabilizer in PVC product.
Current lead heat stabilizer, organo-tin het stabilizer etc. with good heat endurance, but because high price, toxicity are caused
Their use is increasingly restricted.And conventional calcium stearate/zinc heat stabilizer is generally required and other auxiliary heat are steady
Determining agent such as polyalcohol, phosphite ester, beta-diketon compound use can just significantly improve the heat endurance of PVC, but influence PVC product
Initial stage heat endurance simultaneously improve financial cost.Therefore study and develop the substitution of Multifunction calcium zinc heat stabilizer or portion
Dividing the current heat stabilizer of substitution turns into urgent problem.
In this research with zinc nitrate hexahydrate and 2-methylimidazole as development of raw materials calcium stearate/zinc stearate/2- methyl
Imidazoles zinc salt composite thermal stabilizer, the composite thermal stabilizer significantly improves initial stage and the long-term thermal stability that can significantly change a social system product.
Synthetic method of the present invention is simple, and solvent recoverable meets the demand of energy-saving and emission-reduction.
The content of the invention
The technical problem of solution：To solve the problems of PVC heat stabilizer product on existing market, the present invention is provided
A kind of 2-methylimidazole zinc salt and its preparation method and application, prepared 2-methylimidazole zinc salt and calcium stearate and stearic acid
Calcium zinc salt is compounded, and has obtained all very excellent green Ca-Zn composite heat stabilizer of a kind of initial stage and long-term thermal stability.
Technical scheme：A kind of 2-methylimidazole zinc salt, structural formula is：
The preparation method of above-mentioned 2-methylimidazole zinc salt, preparation process is：Take after zinc nitrate hexahydrate is dissolved in solvent orange 2 A and add
To in reaction vessel, 15~30 DEG C are warming up to, by 2-methylimidazole and catalyst B is by zinc nitrate hexahydrate, 2-methylimidazole and urges
The mol ratio of agent B is 1:(2~16):(2~45) are dissolved in solvent orange 2 A, and add to reaction vessel, and 10 are reacted under said temperature
Centrifugation after~60min, deionized water be washed to it is neutral, be dried overnight at 65 DEG C, obtain white solid 2-methylimidazole zinc salt；Institute
It is at least one in DMF, methyl alcohol and deionized water with solvent orange 2 A, total mole number used is six water nitre twice
157~500 times of sour zinc molal quantity.
Preferably, above-mentioned solvent orange 2 A is deionized water, wherein total mole number used is zinc nitrate hexahydrate molal quantity twice
157~500 times.
Preferably, above-mentioned catalyst B is ammoniacal liquor or triethylamine, wherein zinc nitrate hexahydrate, 2-methylimidazole and catalyst B
Mol ratio is 1:2:32 times.
Preferably, above-mentioned reaction temperature is 20 DEG C, and the reaction time is 10min.
Preferably, application of the above-mentioned 2-methylimidazole zinc salt in PVC heat stabilizer.
PVC heat stabilizer, including described 2-methylimidazole zinc salt.
Preferably, above-mentioned PVC heat stabilizer, also including calcium stearate and zinc stearate, wherein calcium stearate, stearic acid
Zinc, 2-methylimidazole zinc salt in mass ratio 4~3:(0.8~0):(0.2~1) compound.
Preferably, above-mentioned PVC heat stabilizer, wherein calcium stearate, zinc stearate, 2-methylimidazole zinc salt are in mass ratio
4:0.7:0.3。
Beneficial effect：1. the HCl additions generation quaternary ammonium for being produced when the tertiary amine atom of electron rich and PVC thermal degradations in imidazoles
Salt, can effectively reduce the acidity of system；The conjugated polyene structure addition that polynary double bond is produced with thermal degradation in PVC, prevents it from entering
One step increases and shortens conjugated polyene segment, can significantly mitigate its coloring.
2. with the d tracks in zinc atom as bridge, two part connections are so as to form a big π keys conjugated body for ring-type
System, the system：On the one hand the free radical activity center of capture unstable chlorine atom is increased, is formed under resonant interaction and more stablized
Free radical intermediate；On the other hand, the heat stabilizer can be chemically crosslinked with the PVC free radicals in degraded, can be notable
The initial stage of transformation of the way product and long-term thermal stability.
3. synthetic method of the present invention is simple, and solvent recoverable meets the demand of energy-saving and emission-reduction.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of 2-methylimidazole zinc salt；
Fig. 2 is X-ray powder diffraction (XRD) spectrogram of 2-methylimidazole zinc salt.
Specific embodiment
It is not directed to partly same as the prior art in text or can be realized using prior art.Following is the present invention
Preferred embodiment, but the present invention is also not limited to following only embodiment, is slightly modified in embodiment and also will be regarded as this
The protection domain of invention.
Embodiment 1
(1) 23.79g (molecular weight 297.49,80mmol) zinc nitrate hexahydrates are taken and 105.20g deionized waters is added to reaction
In container, 13.14g (molecular weight 82.10,160mmol) 2-methylimidazole is completely dissolved in 164.40g (mass fraction 25-
28%) added after ammoniacal liquor in above-mentioned reactor, be warming up to 20 DEG C, centrifugation, deionized water are washed to neutrality, 65 after reaction 10min
It is dried overnight at DEG C, obtains white solid 2-methylimidazole zinc salt；
(2) 9.6g calcium stearates, 1.68g zinc stearates and 0.72g 2-methylimidazoles zinc salt are compounded, obtains calcium zinc and answer
Close heat stabilizer.
The infrared spectrogram of 2-methylimidazole zinc salt manufactured in the present embodiment is shown in Fig. 1.3129 and 2972cm in Fig. 1-1Punishment
Do not occur C-H stretching vibration absworption peaks, 1584cm in phenyl ring and imidazoles-1There are C=N stretching vibration absworption peaks in place, 600-
500cm-1There is stretching vibration and flexural vibrations characteristic peak, 423cm in the big π keys conjugated system of ring-type in place-1There are Zn-N and stretches in place
Contracting vibration absorption peak, 2-methylimidazole zinc salt is generated after showing zinc nitrate hexahydrate and 2-methylimidazole reaction.The present embodiment system
X-ray powder diffraction (XRD) spectrogram of standby 2-methylimidazole zinc salt is shown in Fig. 2.Good ZIF- is presented as seen from Figure 2
8 characteristic peaks：{ 110 }, { 200 }, { 211 }, { 220 }, { 310 } and { 222 }, and crystallinity is all higher.Following examples prepare 2-
Methylimidazole zinc salt has infrared spectrum and XRD spectra substantially the same manner as Example 1, no longer specifically describes.
Embodiment 2
(1) 23.79g (molecular weight 297.49,80mmol) zinc nitrate hexahydrates are taken and 121.70g deionized waters is added to reaction
In container, 13.14g (molecular weight 82.10,160mmol) 2-methylimidazole is completely dissolved in 128.30g (mass fraction 25-
28%) added after ammoniacal liquor in above-mentioned reactor, be warming up to 20 DEG C, centrifugation, deionized water are washed to neutrality, 65 after reaction 30min
It is dried overnight at DEG C, obtains white solid 2-methylimidazole zinc salt；
(2) 9.6g calcium stearates, 0.72g zinc stearates and 1.68g 2-methylimidazoles zinc salt are compounded, obtains calcium zinc and answer
Close heat stabilizer.
Embodiment 3
(1) 23.79g (molecular weight 297.49,80mmol) zinc nitrate hexahydrates are taken and 105.20g deionized waters is added to reaction
In container, 13.14g (molecular weight 82.10,160mmol) 2-methylimidazole is completely dissolved in 164.40g (mass fraction 25-
28%) added after ammoniacal liquor in above-mentioned reactor, be warming up to 20 DEG C, centrifugation, deionized water are washed to neutrality, 65 after reaction 60min
It is dried overnight at DEG C, obtains white solid 2-methylimidazole zinc salt；
(2) 9.6g calcium stearates, 1.20g zinc stearates and 1.20g 2-methylimidazoles zinc salt are compounded, obtains calcium zinc and answer
Close heat stabilizer.
Embodiment 4
(1) 23.79g (molecular weight 297.49,0.08mol) zinc nitrate hexahydrates are taken and 105.20g deionized waters is added to instead
Answer in container, 105.09g (molecular weight 82.10,1.28mol) 2-methylimidazole is completely dissolved in 164.40g (mass fraction 25-
28%) added after ammoniacal liquor in above-mentioned reactor, be warming up to 20 DEG C, centrifugation, deionized water are washed to neutrality, 65 after reaction 30min
It is dried overnight at DEG C, obtains white solid 2-methylimidazole zinc salt；
(2) 9.6g calcium stearates and 2.40g 2-methylimidazoles zinc salt are compounded, obtains Ca-Zn composite heat stabilizer.
Embodiment 5
(1) 23.79g (molecular weight 297.49,80mmol) zinc nitrate hexahydrates are taken and 105.20g deionized waters is added to reaction
In container, 52.54g (molecular weight 82.10,0.64mol) 2-methylimidazole is completely dissolved in 164.40g (mass fraction 25-
28%) added after ammoniacal liquor in above-mentioned reactor, be warming up to 20 DEG C, centrifugation, deionized water are washed to neutrality, 65 after reaction 60min
It is dried overnight at DEG C, obtains white solid 2-methylimidazole zinc salt；
(2) 9.00g calcium stearates, 2.10g zinc stearates and 0.90g 2-methylimidazoles zinc salt are compounded, obtains calcium zinc and answer
Close heat stabilizer.
Embodiment 6
(1) 23.79g (molecular weight 297.49,80mmol) zinc nitrate hexahydrates are taken and 489.06g deionized waters is added to reaction
In container, 52.54g (molecular weight 82.10,0.64mol) 2-methylimidazole is completely dissolved in 230.94g (mass fraction 25-
28%) added after ammoniacal liquor in above-mentioned reactor, be warming up to 20 DEG C, centrifugation, deionized water are washed to neutrality, 65 after reaction 60min
It is dried overnight at DEG C, obtains white solid 2-methylimidazole zinc salt；
(2) 9.00g calcium stearates, 1.50g zinc stearates and 1.50g 2-methylimidazoles zinc salt are compounded, obtains calcium zinc and answer
Close heat stabilizer.
Embodiment 7
(1) 22g (molecular weight 297.49,73.92mmol) zinc nitrate hexahydrates are taken and 133.21g deionized waters is added to reaction
In container, by 36.51g (molecular weight 82.10,444.71mmol) 2-methylimidazole, 15.18g (molecular weight 101.19,
During 150mmol) triethylamine is completely dissolved in after 532.95g deionized waters and adds above-mentioned reactor, 20 DEG C are warming up to, react 60min
Afterwards centrifugation, deionized water be washed to it is neutral, be dried overnight at 65 DEG C, obtain white solid 2-methylimidazole zinc salt；
(2) 9.6g calcium stearates, 0.90g zinc stearates and 2.10g 2-methylimidazoles zinc salt are compounded, obtains calcium zinc and answer
Close heat stabilizer.
Embodiment 8
(1) 22g (molecular weight 297.49,73.92mmol) zinc nitrate hexahydrates are taken and 133.21g deionized waters is added to reaction
In container, by 36.51g (molecular weight 82.10,444.71mmol) 2-methylimidazole, 15.18g (molecular weight 101.19,
During 150mmol) triethylamine is completely dissolved in after 532.95g deionized waters and adds above-mentioned reactor, 20 DEG C are warming up to, react 30min
Afterwards centrifugation, deionized water be washed to it is neutral, be dried overnight at 65 DEG C, obtain white solid 2-methylimidazole zinc salt；
(2) 9.6g calcium stearates and 2.40g 2-methylimidazoles zinc salt are compounded, obtains Ca-Zn composite heat stabilizer.
Comparative example 1：
By calcium zinc heat stabilizer conventional in the market with homemade calcium zinc heat stabilizer in the same same consumption of formula
In the case of (solid calcium zinc amount), compare the thermal stability of its PVC product.
Experimental group 1:
The experimental group 1 of table 1 is constituted
| Raw material | Consumption (g) |
| PVC | 40 |
| DOTP | 20 |
| Calcium stearate | 0.96 |
| Zinc stearate | 0.06 |
| Liquid Ca-Zn composite heat stabilizer prepared by embodiment 1 | 0.18 |
Contrast groups 1:
The contrast groups 1 of table 2 are constituted
Contrast groups 2:
The contrast groups 2 of table 3 are constituted
| Raw material | Consumption (g) |
| PVC | 40 |
| DOTP | 16 |
| Calcium stearate | 0.96 |
| Zinc stearate | 0.24 |
Contrast groups 3:
The contrast groups 3 of table 4 are constituted
| Raw material | Consumption (g) |
| PVC | 40 |
| DOTP | 20 |
| Domestic commercially available Ca-Zn composite heat stabilizer | 1.2 |
Contrast groups 4:
The contrast groups 4 of table 5 are constituted
| Raw material | Consumption (g) |
| PVC | 40 |
| DOTP | 16 |
| Domestic commercially available Ca-Zn composite heat stabilizer | 1.2 |
Static heat stability is tested：The material mixing for being respectively formulated experimental group 1, experimental group 2, contrast groups 1 and contrast groups 4
Uniformly, take 60.0g 160-165 DEG C on the torque rheometer, plasticate 3min under rotating speed 40r/min, is pressed into the test piece of 1mm thickness.
The heat endurance of product is investigated according to ISO 182-1-1990 Congo Red tests methods and ISO 305-1990 (E).
On the premise of plasticizing capacity is not influenceed, self-control liquid Ca-Zn composite heat stabilizer has been investigated to PVC heat endurances
Influence.The heat endurance experimental result of experimental group 1, experimental group 2, contrast groups 1 and contrast groups 4 is as shown in table 6.In summary tie
Fruit understands：With domestic commercially available Ca-Zn composite heat stabilizer and calcium stearate/zinc stearate compound thermal stable phase ratio, liquid calcium is made by oneself
Zn composite heat stabilizer has more excellent long-term thermal stability, and mechanical property is had no adverse effects.
The experimental group of table 6 is contrasted with the static heat stability of contrast groups heat stabilizer
Claims (9)
1. a kind of 2-methylimidazole zinc salt, it is characterised in that structural formula is：
2. the preparation method of 2-methylimidazole zinc salt described in claim 1, it is characterised in that preparation process is：Take zinc nitrate hexahydrate
It is added in reaction vessel after being dissolved in solvent orange 2 A, is warming up to 15~30 DEG C, 2-methylimidazole and catalyst B is pressed into six water nitric acid
The mol ratio of zinc, 2-methylimidazole and catalyst B is 1:(2~16):(2~45) are dissolved in solvent orange 2 A, and add to reaction vessel
In, reacted under said temperature centrifugation after 10~60min, deionized water be washed to it is neutral, be dried overnight at 65 DEG C, obtain white solid
Body 2-methylimidazole zinc salt；Solvent for use A is at least one in DMF, methyl alcohol and deionized water, twice
Total mole number used is 157~500 times of zinc nitrate hexahydrate molal quantity.
3. the preparation method of 2-methylimidazole zinc salt according to claim 2, it is characterised in that the solvent orange 2 A is deionization
Water, total mole number used is 157~500 times of zinc nitrate hexahydrate molal quantity twice.
4. the preparation method of 2-methylimidazole zinc salt according to claim 2, it is characterised in that the catalyst B be ammoniacal liquor or
The mol ratio of triethylamine, wherein zinc nitrate hexahydrate, 2-methylimidazole and catalyst B is 1:2:32 times.
5. the preparation method of 2-methylimidazole zinc salt according to claim 2, it is characterised in that reaction temperature is 20 DEG C, reaction
Time is 10min.
6. application of the 2-methylimidazole zinc salt in PVC heat stabilizer described in claim 1.
7.PVC heat stabilizers, it is characterised in that including the 2-methylimidazole zinc salt described in claim 1.
8. PVC heat stabilizer according to claim 7, it is characterised in that also including calcium stearate and zinc stearate, wherein
Calcium stearate, zinc stearate, 2-methylimidazole zinc salt in mass ratio 4~3:(0.8~0):(0.2~1) compound.
9. PVC heat stabilizer according to claim 8, it is characterised in that the calcium stearate, zinc stearate, 2- methyl miaows
Azoles zinc salt is 4 in mass ratio:0.7:0.3.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108383861A (en) * | 2018-02-13 | 2018-08-10 | 浙江工业大学 | It is a kind of containing Zn complex and preparation method and to include the plastic additive containing Zn complex |
| CN108400324A (en) * | 2018-03-07 | 2018-08-14 | 华南师范大学 | A kind of lithium ion battery negative material zinc manganate nanometer rods and preparation method thereof |
| CN108864602A (en) * | 2018-07-17 | 2018-11-23 | 广州广化塑料管道有限公司 | Nano combined heat stabilizer of eutectic applied to PVC material and preparation method thereof |
| RU2719596C1 (en) * | 2019-09-25 | 2020-04-21 | Общество с ограниченной ответственностью "Инжиниринговый химико-технологический центр" (ООО "ИХТЦ") | Fast and scalable method of producing microporous zinc 2-methylimidazolate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108383861A (en) * | 2018-02-13 | 2018-08-10 | 浙江工业大学 | It is a kind of containing Zn complex and preparation method and to include the plastic additive containing Zn complex |
| CN108383861B (en) * | 2018-02-13 | 2021-01-01 | 浙江工业大学 | Zinc-containing complex, preparation method thereof and plastic auxiliary agent containing zinc-containing complex |
| CN108400324A (en) * | 2018-03-07 | 2018-08-14 | 华南师范大学 | A kind of lithium ion battery negative material zinc manganate nanometer rods and preparation method thereof |
| CN108400324B (en) * | 2018-03-07 | 2020-07-10 | 华南师范大学 | Lithium ion battery cathode material zinc manganate nanorod and preparation method thereof |
| CN108864602A (en) * | 2018-07-17 | 2018-11-23 | 广州广化塑料管道有限公司 | Nano combined heat stabilizer of eutectic applied to PVC material and preparation method thereof |
| RU2719596C1 (en) * | 2019-09-25 | 2020-04-21 | Общество с ограниченной ответственностью "Инжиниринговый химико-технологический центр" (ООО "ИХТЦ") | Fast and scalable method of producing microporous zinc 2-methylimidazolate |
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