CN105801607B - A kind of PVC heat stabilizer and preparation method thereof - Google Patents
A kind of PVC heat stabilizer and preparation method thereof Download PDFInfo
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- CN105801607B CN105801607B CN201610243133.0A CN201610243133A CN105801607B CN 105801607 B CN105801607 B CN 105801607B CN 201610243133 A CN201610243133 A CN 201610243133A CN 105801607 B CN105801607 B CN 105801607B
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- 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 System
- C07F3/06—Zinc compounds
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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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The present invention relates to PVC fields, more particularly to a kind of PVC heat stabilizer and preparation method thereof.A kind of PVC heat stabilizer, the heat stabilizer chemical formula are (C12H12N2S)(C5H6O4) Zn, wherein, C5H6O4For glutarate, C12H12N2S is two (4 ylmethyl of pyridine) sulfanes.The novel PVC heat stabilizer synthetic method of the present invention is simple, and stability is good, nontoxic, environmentally friendly without any heavy metal, and special structure can effectively adsorb free HCl, has very excellent thermostability energy.
Description
Technical field
The present invention relates to PVC fields, more particularly to a kind of PVC heat stabilizer and preparation method thereof.
Background technology
Polyvinyl chloride (PVC) is the second largest general-purpose plastics that yield is only second to polyethylene, has high intensity, corrosion-resistant, difficult
The advantages that combustion and insulating properties, the transparency, it is widely used in industrial building, agricultural, daily necessities, packaging, ceremony, public utilities etc.
Field.But due to containing unstable chlorine atom on (PVC) macromolecular chain, start to decompose abjection HCl, molecule at 100 DEG C
Being formed immediately on chain has jerky conjugated polyene structure, product discoloration.HCl has catalytic action to the degradation of PVC, HCl's
Accumulation greatly accelerates the degradation of PVC so that the acceptance of materials is drastically deepened, and physical mechanical property declines or even carbonization is lost and used
Value.Therefore, heat stabilizer is the necessary additive in PVC material, but the often suction to HCl of existing PVC heat stabilizer
It is attached poor, therefore there is an urgent need for can send a kind of heat stabilizer that can effectively adsorb HCl.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of PVC heat stabilizer.
It is another object of the present invention to provide the preparation methods of above-mentioned PVC heat stabilizer.
A kind of PVC heat stabilizer, the heat stabilizer chemical formula are (C12H12N2S)(C5H6O4) Zn, wherein, C5H6O4For penta 2
Acid group, C12H12N2S be two (pyridin-4-yl methyl) sulfanes, the heat stabilizer be anorthic system, P-1 space groups, cell parameter
Forα=83.58 (3) °, β=75.03 (5) °, γ=78.71
(2) °,
The preparation method of above-mentioned PVC heat stabilizer is：By organic compound two (pyridin-4-yl methyl) sulfane, penta 2
Acid and zinc nitrate are dissolved among the mixed solvent of dimethylformamide and ethyl alcohol, wherein the volume ratio of dimethylformamide and ethyl alcohol
For 2:1, be stirred at room temperature to form mixed liquor A, then the mixed liquor A is reacted at 55 DEG C reflux 36 it is small when mixed
Liquid B, slow cooling obtains the PVC heat stabilizer after the mixed liquid B is finally heated reaction under hydrothermal conditions.
Wherein, two (pyridin-4-yl methyl) sulfane English are：bis(pyridin-4-ylmethyl)sulfane.
Further, the heating temperature is 160 DEG C~180 DEG C, when the heating reaction time is 24~48 small.
Further, the cooling is down to room temperature for 2 DEG C/h~5 DEG C/h.
Further, the molar ratio of described two (pyridin-4-yl methyl) sulfanes, glutaric acid and zinc nitrate is 1:1:1.
Application of the above-mentioned heat stabilizer in PVC.
The present invention has the advantages that：
The PVC heat stabilizer synthetic method of the present invention is simple, and stability is good, nontoxic, environmentally friendly without any heavy metal,
Special structure can effectively adsorb free HCl, have very excellent thermostability energy.
Description of the drawings
Fig. 1 is the heat stabilizer of the present invention with the coordination context diagram of metal center Zn.
Specific embodiment
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It is not limitation of the invention.
Embodiment 1
0.1mmol bis- (pyridin-4-yl methyl) sulfane, 0.1mmol glutaric acids and 0.1mmol zinc nitrates are dissolved in 10mL bis-
Among the mixed solvent of methylformamide and 5mL ethyl alcohol, mixed liquor A is formed after dissolving is stirred at room temperature, it then will be described mixed
Close liquid A react at 55 DEG C flow back 36 it is small when obtain mixed liquid B, mixed liquid B is then transferred to polytetrafluoroethylene (PTFE) reaction under high pressure
In kettle, place it in 170 DEG C of baking ovens reaction 36 it is small when, be down to room temperature with 5 DEG C/h afterwards and the thermostabilization be obtained by filtration
Agent, yield are 71.4% (being based on zinc).
Then above-mentioned heat stabilizer is subjected to structural characterization.
The X ray diffracting data of the heat stabilizer is to be visited in Bruker Smart Apex CCD faces on diffractometer, uses MoKα
RadiationIt is collected with ω scan modes and carries out Lp factor corrections, absorption correction uses SADABS programs.With
Then direct method solution structure is obtained whole non-hydrogen atom coordinates with difference Fourier method, and obtains hydrogen atom with theoretical hydrogenation method
PositionStructure is modified with least square method.Evaluation work uses SHELXTL program bags in PC machine
It completes.The heat stabilizer structure is shown in Fig. 1.
Parsing is understood after tested, which is (C12H12N2S)(C5H6O4) Zn, wherein, C5H6O4For penta 2
Acid group, C12H12N2S be two (pyridin-4-yl methyl) sulfanes, the heat stabilizer be anorthic system, P-1 space groups, cell parameter
Forα=83.58 (3) °, β=75.03 (5) °, γ=78.71
(2) °,Z=4.
From the point of view of crystal structure, which belongs to anorthic system, P-1 space groups, contains one in the asymmetric cell
A Zn atoms, two (pyridin-4-yl methyl) sulfanes and wherein glutaric acid, a Zn atom take the octahedral mould of 6 coordinations
Formula and 4 O atom coordinations and 2 N Atomic coordinates, wherein 4 O atoms take the pattern of chelating ligands, and 2 N atoms are taken
The pattern of monodentate ligand, as shown in Figure 1；N atoms on the pyridyl group at two (pyridin-4-yl methyl) sulfane both ends, and penta 2
Zn atoms by the way of 2 connections are extended and connect into a kind of special three-dimensional structure by acid both ends oxygen atom, and this spy
Different three-dimensional structure is conducive to the absorption of HCl so that heat stabilizer of the invention has good performance.
Embodiment 2
0.1mmol bis- (pyridin-4-yl methyl) sulfane, 0.1mmol glutaric acids and 0.1mmol zinc nitrates are dissolved in 10mL bis-
Among the mixed solvent of methylformamide and 5mL ethyl alcohol, mixed liquor A is formed after dissolving is stirred at room temperature, it then will be described mixed
Close liquid A react at 55 DEG C flow back 36 it is small when obtain mixed liquid B, mixed liquid B is then transferred to polytetrafluoroethylene (PTFE) reaction under high pressure
In kettle, place it in 160 DEG C of baking ovens reaction 48 it is small when, be down to room temperature with 2 DEG C/h afterwards and the thermostabilization be obtained by filtration
Agent, yield are 64.1% (being based on zinc).
Embodiment 3
0.1mmol bis- (pyridin-4-yl methyl) sulfane, 0.1mmol glutaric acids and 0.1mmol zinc nitrates are dissolved in 10mL bis-
Among the mixed solvent of methylformamide and 5mL ethyl alcohol, mixed liquor A is formed after dissolving is stirred at room temperature, it then will be described mixed
Close liquid A react at 55 DEG C flow back 36 it is small when obtain mixed liquid B, mixed liquid B is then transferred to polytetrafluoroethylene (PTFE) reaction under high pressure
In kettle, place it in 180 DEG C of baking ovens reaction 24 it is small when, be down to room temperature with 3 DEG C/h afterwards and the thermostabilization be obtained by filtration
Agent, yield are 48.7% (being based on zinc).
Then the heat stabilizer obtained by above-described embodiment is prepared into PVC material by additive amount for the 3% of weight fraction.It should
The preparation method of PVC material is adopted as the common method of the art, is not described in detail in the present invention.
Wherein, the comparative example PVC material below in performance test is to replace the present invention using the common heat stabilizer in market
Heat stabilizer, the dosage in PVC material is consistent with the present invention.
Then by the PVC material of above-mentioned gained according to congo red method as defined in GB/T 2917.1-2002, in 200 DEG C of progress
Heat stability testing.Table 1 is test performance table.
1 congo red method of table tests table
| Temperature-time ts(min) | |
| Heat stabilizer of the present invention | 108.2 |
| Comparative example | 78.9 |
Be with the addition of it can be seen from 1 data of table the PVC material of heat stabilizer of the present invention due to its can effectively adsorb it is free
HCl, therefore with good thermostable effect, effect is much better than existing common PVC heat stabilizer.
Then the PVC material of above-mentioned gained is tested according to whiteness method as defined in GB/T 15595-2008.Table 2 is
Test performance table.
2 whiteness method of table tests table
It can be seen from 2 data of table using heat stabilizer of the present invention PVC material for 24 hours, 48h, 72h and 120h when sample
Product whiteness is above the sample whiteness of comparative example PVC material.With the extension of time, the comparison that the sample whiteness of comparative example reduces
Substantially, in 120h the sample whiteness of comparative example for 62.3%, and use the PVC material whiteness of heat stabilizer of the present invention for
85.7%, this illustrates that the heat stabilizer of the present invention similarly has good weatherability.
Embodiment described above only expresses embodiments of the present invention, and description is more specific and detailed, but can not
Therefore the limitation to the scope of the claims of the present invention is interpreted as, as long as the skill obtained using the form of equivalent substitution or equivalent transformation
Art scheme should all be fallen within the scope and spirit of the invention.
Claims (2)
1. a kind of PVC heat stabilizer, it is characterised in that：The heat stabilizer chemical formula is (C12H12N2S)(C5H6O4) Zn, wherein,
C5H6O4For glutarate, C12H12N2S is two (pyridin-4-yl methyl) sulfanes；
The heat stabilizer is anorthic system, and P-1 space groups, cell parameter is α=83.58 (3) °, β=75.03 (5) °, γ=78.71 (2) °,
The heat stabilizer synthesizes in accordance with the following methods：By organic compound two (pyridin-4-yl methyl) sulfane, glutaric acid and nitre
Sour zinc is dissolved among the mixed solvent of dimethylformamide and ethyl alcohol, and wherein the volume ratio of dimethylformamide and ethyl alcohol is 2:1,
Be stirred at room temperature to form mixed liquor A, then the mixed liquor A is reacted at 55 DEG C reflux 36 it is small when obtain mixed liquid B, most
Slow cooling obtains the PVC heat stabilizer after the mixed liquid B is heated reaction under hydrothermal conditions afterwards；
The heating temperature is 160 DEG C~180 DEG C, when the heating reaction time is 24~48 small；
The cooling is down to room temperature for 2 DEG C/h~5 DEG C/h；
The molar ratio of described two (pyridin-4-yl methyl) sulfanes, glutaric acid and zinc nitrate is 1:1:1.
2. application of the heat stabilizer described in claim 1 in PVC.
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| CN105801607B true CN105801607B (en) | 2018-05-22 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1253144A (en) * | 1998-09-16 | 2000-05-17 | 莫顿国际股份有限公司 | Combination of organic sulfide and zinc salt of sulfhydryl ester used as thermal stabilizer in PVC processing |
| US20020044968A1 (en) * | 1996-10-28 | 2002-04-18 | General Mills, Inc. | Embedding and encapsulation of sensitive components into a matrix to obtain discrete controlled release particles |
| CN102993220A (en) * | 2012-12-06 | 2013-03-27 | 洛阳师范学院 | 5-bromoisophthalic acid zinc complex and preparation method thereof |
| CN103183690A (en) * | 2011-12-31 | 2013-07-03 | 深圳市志海实业有限公司 | Calcium zinc heat stabilizer used for PVC, zinc-containing compound and application |
| CN104262368A (en) * | 2014-10-04 | 2015-01-07 | 刘国政 | Coordination polymer regulated by aliphatic polycarboxylic ligand side group and preparation method of coordination polymer |
-
2016
- 2016-04-19 CN CN201610243133.0A patent/CN105801607B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020044968A1 (en) * | 1996-10-28 | 2002-04-18 | General Mills, Inc. | Embedding and encapsulation of sensitive components into a matrix to obtain discrete controlled release particles |
| CN1253144A (en) * | 1998-09-16 | 2000-05-17 | 莫顿国际股份有限公司 | Combination of organic sulfide and zinc salt of sulfhydryl ester used as thermal stabilizer in PVC processing |
| CN103183690A (en) * | 2011-12-31 | 2013-07-03 | 深圳市志海实业有限公司 | Calcium zinc heat stabilizer used for PVC, zinc-containing compound and application |
| CN102993220A (en) * | 2012-12-06 | 2013-03-27 | 洛阳师范学院 | 5-bromoisophthalic acid zinc complex and preparation method thereof |
| CN104262368A (en) * | 2014-10-04 | 2015-01-07 | 刘国政 | Coordination polymer regulated by aliphatic polycarboxylic ligand side group and preparation method of coordination polymer |
Non-Patent Citations (1)
| Title |
|---|
| Complex Compounds Based on 1-Isopropenylimidazoles and -pyrazole;Zyryanova, I. A. et al;《Russian Journal of General Chemistry》;20051231;第75卷;第1283-1289页 * |
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Inventor after: Cai Jintian Inventor before: Lai Shuxing |
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Effective date of registration: 20180425 Address after: 528100 9 North factory building of hardware workshop, 9-2-1, C, 9-2-1, Sanshui Park, Sanshui center, Guangdong. Applicant after: Guangdong common force building materials Co., Ltd. Address before: 528100 1509, room 8, Royal Longwan garden, 28 Xiqing Avenue, Southwest District, Sanshui District, Foshan, Guangdong Applicant before: Lai Shuxing |
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Denomination of invention: A PVC heat stabilizer and its preparation method Effective date of registration: 20200826 Granted publication date: 20180522 Pledgee: Guangdong Nanhai Rural Commercial Bank branch branch of Limited by Share Ltd. Pledgor: GUANGDONG GONGLI BUILDING MATERIALS Co.,Ltd. Registration number: Y2020440000238 |
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