CN106188938A - A kind of powder body zinc-base composite thermal stabilizer and preparation method - Google Patents
A kind of powder body zinc-base composite thermal stabilizer and preparation method Download PDFInfo
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- CN106188938A CN106188938A CN201610550292.5A CN201610550292A CN106188938A CN 106188938 A CN106188938 A CN 106188938A CN 201610550292 A CN201610550292 A CN 201610550292A CN 106188938 A CN106188938 A CN 106188938A
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Abstract
The present invention relates to a kind of powder body zinc-base composite thermal stabilizer and preparation method, particularly relate to a kind of polyvinyl-chloride use powder body zinc-base composite thermal stabilizer and preparation method, described composite thermal stabilizer is processed by the component of following weight portion: zinc-base coordination compound 35 55 parts, zinc burns inhibitor 10 20 parts, auxiliary heat stabilizer 10 20 parts, compatilizer 5 10 parts, inorganic assistant 5 15 parts, butyl 5 10 parts, described zinc-base coordination compound is zinc acetylacetonate, zinc glycinate, p-tert-butyl benzoic acid zinc and TGA are against the compositions of thioesters zinc, described auxiliary heat stabilizer is three (glycidyl) chlorinated isocyanurates, the arbitrary proportion mixture of any two kinds in methyl-silicone oil and hydrazino benzyl formate.Compared with existing powder body calcium zinc heat stabilizer, no longer adding fatty acid calcium salt and fatty acid zinc salt in the powder body zinc-base composite thermal stabilizer of the present invention, product is difficult to separate out, and is difficult to bloom, solves current calcium zinc stabilizer and separates out problem at coloured PVC product surface bloom.
Description
Technical field
The present invention relates to a kind of powder body zinc-base composite thermal stabilizer and preparation method, particularly relate to a kind of polyvinyl-chloride use powder
Body zinc-base composite thermal stabilizer and preparation method.
Background technology
The heat stabilizer that China's polrvinyl chloride (PVC) goods industry usage amount is maximum at present is leaded heat stabilizer, uses every year
Amount about reaches 600,000 tons.Along with the whole world is to ecological environmental protection consciousness and the raising of requirement, leaded heat stabilizer will face by completely
The situation of disabling, exploitation efficient green stabilizer has become the major technology bottleneck of restriction PVC product industry sustainable and healthy development.Calcium
Zn composite heat stabilizer is owing to having thermally-stabilised efficiency preferably with to features such as environment shadow are friendly, by the height weight of industrial circle
Depending on, there is good development prospect.
Ca-Zn composite heat stabilizer mainly uses fatty acid calcium salt and fatty acid zinc salt to be main stabilizer at present, is equipped with auxiliary
Stabilizer and lubricant prepare, and Chinese patent CN102321312A discloses a kind of PVC calcium-zinc composite stabilizing agent,
With single fat acid calcium salt and fatty acid zinc salt as main stabilizer, being equipped with brucite, heterocyclic compound etc. is prepared from.China is specially
Profit CN102875930A discloses a kind of calcium-zinc composite stabilizing agent, and this stabilizer is with zinc stearate, calcium stearate and O-phthalic
Based on acid two the most pungent fat, separately add auxiliary stabilizer and lubricant etc. and constitute.Owing to fatty acid calcium salt has serious plate-out,
Fatty acid zinc has serious bloom phenomenon, therefore causes existing calcium-zinc composite stabilizing agent product to there is significantly pressure analysis and bloom
Etc. problem, limit it and extensively apply in PVC field.
Summary of the invention
An object of the present invention is to solve the deficiency that the calcium-zinc composite stabilizing agent product of prior art exists, it is provided that one
Plant powder body zinc-base composite thermal stabilizer, the fatty acid calcium of this composite thermal stabilizer abandoning tradition and fatty acid zinc, select multiple containing
The zinc salt of N, S and phenyl ring is combined, and product is difficult to separate out, and is difficult to bloom, has good initial coloring and long-term thermal stability.
The two of the purpose of the present invention are to provide the preparation method of a kind of powder body zinc-base composite thermal stabilizer.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of powder body zinc-base composite thermal stabilizer, described composite thermal stabilizer is processed by the component of following weight portion:
Zinc-base coordination compound 35-55 part
Zinc burns inhibitor 10-20 part
Auxiliary heat stabilizer 10-20 part
Compatilizer 5-10 part
Inorganic assistant 5-15 part
Butyl 5-10 part；
Described zinc-base coordination compound is that zinc acetylacetonate, zinc glycinate, p-tert-butyl benzoic acid zinc and TGA are against thioesters
The compositions of zinc, described auxiliary heat stabilizer is in three (glycidyl) chlorinated isocyanurates, methyl-silicone oil and hydrazino benzyl formate
The arbitrary proportion mixture of any two kinds.
Preferably, described composite thermal stabilizer is processed by the component of following weight portion:
Zinc-base coordination compound 40-50 part
Zinc burns inhibitor 15-20 part
Auxiliary heat stabilizer 10-15 part
Compatilizer 5-8 part
Inorganic assistant 5-10 part
Butyl 5-8 part.
Preferably, described composite thermal stabilizer is processed by the component of following weight portion:
Zinc-base coordination compound 45 parts
Zinc burns inhibitor 18 parts
Auxiliary heat stabilizer 17 parts
Compatilizer 7.5 parts
Inorganic assistant 8 parts
Butyl 7 parts.
Preferably, the weight portion of described zinc-base coordination compound consists of: zinc acetylacetonate 30-45 part, zinc glycinate 5-15 part,
P-tert-butyl benzoic acid zinc 3-10 part, TGA is against thioesters zinc 2-8 part.
Preferably, described zinc burns inhibitor is tetramethylolmethane two p-tert-butyl benzoic acid ester, sodium citrate and 4A molecular sieve
1:(2 in mass ratio～5): the coordination compound of (3～5).
Preferably, described compatilizer is maleic anhydride monomer graft PVC-g-MAH and in PE wax graft PVC-g-PEW
Any one, or the arbitrary proportion mixture of two kinds.
Preferably, the arbitrary proportion of any two kinds during described inorganic assistant is attapulgite, calcium oxide and sodium bicarbonate
Mixture.
Powder body zinc-base composite thermal stabilizer of the present invention, compounds as main stabilizer, greatly with multiple non-fat race zinc-based compounds
Improve greatly the initial coloring of PVC product, hence it is evident that reduce the bloom problem of aliphatic zinc salt, add zinc and burn inhibitor, logical
Perhydroxyl radical chelation, efficiently suppresses PVC " zinc burning " phenomenon, improves overall processing application and the heat resistance of calcium zinc stabilizer,
Add high molecular auxiliary heat stabilizer, owing to having amino etc. freely, chlorine radical after being degraded by association PVC and double
Alkene structural molecule relic and make PVC stabilisation, improve the thermal stability of PVC system and mechanical performance, improve stabilizer and PVC
Between the compatibility, adding compatilizer can form affine point with organic group, thus increases compatible in PVC of stabilizer
Property, improve stabilization efficiency, add inorganic assistant, the hydrogen chloride of generation in PVC degradation process can be neutralized, improve stable system
Property, and there is good lubricity, and the processing of beneficially PVC, reduce product cost simultaneously, add butyl, permissible
Improve the homogeneity of each component mixing in stabilizer, keep the stability of product quality.It is processed into by the processing technique of the present invention
Zinc-base composite thermal stabilizer, synergism between each component, reach good initial stage and long-time stability, PVC processing characteristics
And good mechanical performance, PVC product initial stage whiteness is good, no blooming.
A kind of preparation method of powder body zinc-base composite thermal stabilizer, described method is carried out as follows:
(1) high velocity fog mix stages: the zinc-base coordination compound of formula ratio, zinc are burnt inhibitor, auxiliary heat stabilizer, compatible
Agent and inorganic assistant are sequentially added in mixer, start stirring, and control rotating speed is 500-650r/min, by butyl with
Vaporific being sprayed onto in compound, spray rate is 2.5-3.5kg/min, and incorporation time is 3-6min clock；
(2) low speed remixes the stage: on the basis of step (1), and adjustment rotating speed is 150-300r/min, mixed on low speed
0.5-3min clock, obtains powder body zinc-base composite thermal stabilizer.
Preferably, in step (1), speed of agitator is 550-600r/min, and butyl spray rate is 3-
3.5kg/min, incorporation time is 3-5min clock；In step (2), speed of agitator is 200-300r/min, and incorporation time is 1-
3min clock.
The invention has the beneficial effects as follows:
(1) compared with existing powder body calcium zinc heat stabilizer, powder body zinc-base composite thermal stabilizer of the present invention no longer adds fat
Fat acid calcium salt and fatty acid zinc salt, product is difficult to separate out, is difficult to bloom, solves current calcium zinc stabilizer in coloured PVC product
Surface bloom separates out problem；
(2) powder body zinc-base composite thermal stabilizer of the present invention, adds Compositional type and contains N, S and the zinc salt of phenyl ring and zinc burning suppression
Agent, the multiple auxiliary agent such as compatilizer, improve existing calcium zinc stabilizer combination property, the heat stabilizer product of the present invention has excellence
Initial stage whiteness and long-time stability, there is the compatibility more preferable with PVC, the synergy between component is more preferable；
(3) powder body zinc-base composite thermal stabilizer of the present invention, uses liquid spray, high low speed to coordinate technique to prepare, product
Uniformity is more preferable, and quality is more stable.
Accompanying drawing explanation
Fig. 1: various sample static heat stabilization time and Congo red time result figure.
Detailed description of the invention
Below by specific embodiment, technical scheme is described in further detail.
Embodiment 1
A kind of powder body zinc-base composite thermal stabilizer, described composite thermal stabilizer is processed from following component: with zinc-base
Thing 35g, zinc burn inhibitor 10g, auxiliary heat stabilizer 10g, compatilizer 5g, inorganic assistant 5g, butyl 5g；Described zinc
Basigamy compound is mixed by following component: zinc acetylacetonate 30g, zinc glycinate 5g, p-tert-butyl benzoic acid zinc 3g and sulfydryl
Acetic acid is against thioesters zinc 2g, and described auxiliary heat stabilizer is three (glycidyl) chlorinated isocyanurates 5g and methyl-silicone oil 5g composition, zinc
Burning inhibitor is tetramethylolmethane two p-tert-butyl benzoic acid ester, sodium citrate and the coordination compound of 4A molecular sieve 1:2:3 in mass ratio,
Compatilizer is maleic anhydride monomer graft PVC-g-MAH, and inorganic assistant is the equal proportion mixture of attapulgite and calcium oxide.
Accurately weigh zinc-base coordination compound, zinc burns inhibitor, auxiliary heat stabilizer, compatilizer and inorganic assistant, is sequentially added into
In mixer, starting stirring, control rotating speed is 500r/min, is sprayed onto in compound with vaporific by butyl, sprays
Speed is 2.5kg/min, and incorporation time is 6min clock, and then adjusting rotating speed is 150r/min, and mixed on low speed 6min clock obtains powder
Body zinc-base composite thermal stabilizer.
Embodiment 2
A kind of powder body zinc-base composite thermal stabilizer, described composite thermal stabilizer is processed from following component: with zinc-base
Thing 55g, zinc burn inhibitor 20g, auxiliary heat stabilizer 20g, compatilizer 10g, inorganic assistant 15g, butyl 10g；Institute
State zinc-base coordination compound to be mixed by following component: zinc acetylacetonate 45g, zinc glycinate 15g, p-tert-butyl benzoic acid zinc 10g
With TGA against thioesters zinc 8g, described auxiliary heat stabilizer is three (glycidyl) chlorinated isocyanurates 10g and carbazic acid benzyl
Ester 10g forms, and zinc burns inhibitor by tetramethylolmethane two p-tert-butyl benzoic acid ester, sodium citrate and 4A molecular sieve in mass ratio 1:
The coordination compound of 5:5, compatilizer is PE wax graft PVC-g-PEW, and inorganic assistant is the equal proportion of attapulgite and sodium bicarbonate
Mixture.
Accurately weigh zinc-base coordination compound, zinc burns inhibitor, auxiliary heat stabilizer, compatilizer and inorganic assistant, is sequentially added into
In mixer, starting stirring, control rotating speed is 650r/min, is sprayed onto in compound with vaporific by butyl, sprays
Speed is 3.5kg/min, and incorporation time is 3min clock, and then adjusting rotating speed is 300r/min, and mixed on low speed 3min clock obtains powder
Body zinc-base composite thermal stabilizer.
Embodiment 3
A kind of powder body zinc-base composite thermal stabilizer, described composite thermal stabilizer is processed from following component: with zinc-base
Thing 40g, zinc burn inhibitor 15g, auxiliary heat stabilizer 10g, compatilizer 5g, inorganic assistant 5g, butyl 5g；Described zinc
Basigamy compound is mixed by following component: zinc acetylacetonate 30g, zinc glycinate 5g, p-tert-butyl benzoic acid zinc 3g and sulfydryl
Acetic acid is against thioesters zinc 2g, and described auxiliary heat stabilizer is three (glycidyl) chlorinated isocyanurates 5g and hydrazino benzyl formate 5g group
Becoming, zinc burns inhibitor joining by tetramethylolmethane two p-tert-butyl benzoic acid ester, sodium citrate and 4A molecular sieve 1:5:5 in mass ratio
Compound, compatilizer is maleic anhydride monomer graft PVC-g-MAH2.5g and PE wax graft PVC-g-PEW2.5g, without machine aided
Agent is the equal proportion mixture of attapulgite and sodium bicarbonate.
Accurately weigh zinc-base coordination compound, zinc burns inhibitor, auxiliary heat stabilizer, compatilizer and inorganic assistant, is sequentially added into
In mixer, starting stirring, control rotating speed is 600r/min, is sprayed onto in compound with vaporific by butyl, sprays
Speed is 3.5kg/min, and incorporation time is 4min, and then adjusting rotating speed is 250r/min, and mixed on low speed 1min obtains powder body zinc
Based composite heat stabilizer.
Embodiment 4
A kind of powder body zinc-base composite thermal stabilizer, described composite thermal stabilizer is processed from following component: with zinc-base
Thing 50g, zinc burn inhibitor 20g, auxiliary heat stabilizer 15g, compatilizer 8g, inorganic assistant 10g, butyl 8g；Described
Zinc-base coordination compound is mixed by following component: zinc acetylacetonate 45g, zinc glycinate 15g, p-tert-butyl benzoic acid zinc 10g and
TGA is against thioesters zinc 8g, and described auxiliary heat stabilizer is methyl-silicone oil 7.5g and hydrazino benzyl formate 7.5g composition, and zinc burns
Inhibitor is by tetramethylolmethane two p-tert-butyl benzoic acid ester, sodium citrate and the coordination compound of 4A molecular sieve 1:2:3 in mass ratio, phase
Holding agent is maleic anhydride monomer graft PVC-g-MAH4g and PE wax graft PVC-g-PEW4g, and inorganic assistant is attapulgite
Equal proportion mixture with sodium bicarbonate.
Accurately weigh zinc-base coordination compound, zinc burns inhibitor, auxiliary heat stabilizer, compatilizer and inorganic assistant, is sequentially added into
In mixer, starting stirring, control rotating speed is 600r/min, is sprayed onto in compound with vaporific by butyl, sprays
Speed is 3.5kg/min, and incorporation time is 4min clock, and then adjusting rotating speed is 250r/min, and mixed on low speed 1min clock obtains powder
Body zinc-base composite thermal stabilizer.
Embodiment 5
A kind of powder body zinc-base composite thermal stabilizer, described composite thermal stabilizer is processed from following component: with zinc-base
Thing 45g, zinc burn inhibitor 18g, auxiliary heat stabilizer 14g, compatilizer 7.5g, inorganic assistant 8g, butyl 7g；Described
Zinc-base coordination compound is mixed by following component: zinc acetylacetonate 38g, zinc glycinate 12g, p-tert-butyl benzoic acid zinc 7g and mercapto
Guanidine-acetic acid is against thioesters zinc 7g, and described auxiliary heat stabilizer is methyl-silicone oil 7g and hydrazino benzyl formate 7g composition, and zinc burns inhibitor
By tetramethylolmethane two p-tert-butyl benzoic acid ester, sodium citrate and the coordination compound of 4A molecular sieve 1:2:3 in mass ratio, compatilizer is
Maleic anhydride monomer graft PVC-g-MAH3g and PE wax graft PVC-g-PEW4.5g, inorganic assistant is attapulgite and carbon
The equal proportion mixture of acid hydrogen sodium.
Accurately weigh zinc-base coordination compound, zinc burns inhibitor, auxiliary heat stabilizer, compatilizer and inorganic assistant, is sequentially added into
In mixer, starting stirring, control rotating speed is 500r/min, is sprayed onto in compound with vaporific by butyl, sprays
Speed is 3kg/min, and incorporation time is 6min clock, and then adjusting rotating speed is 300r/min, and mixed on low speed 0.5min clock obtains powder
Body zinc-base composite thermal stabilizer.
Embodiment 6
A kind of powder body zinc-base composite thermal stabilizer, described composite thermal stabilizer is processed from following component: with zinc-base
Thing 38g, zinc burn inhibitor 18g, auxiliary heat stabilizer 12g, compatilizer 8g, inorganic assistant 10g, butyl 8g；Described
Zinc-base coordination compound is mixed by following component: zinc acetylacetonate 32g, zinc glycinate 6g, p-tert-butyl benzoic acid zinc 6g and mercapto
Guanidine-acetic acid is against thioesters zinc 5g, and described auxiliary heat stabilizer is methyl-silicone oil 6g and hydrazino benzyl formate 6g composition, and zinc burns inhibitor
By tetramethylolmethane two p-tert-butyl benzoic acid ester, sodium citrate and the coordination compound of 4A molecular sieve 1:2:5 in mass ratio, compatilizer is
Maleic anhydride monomer graft PVC-g-MAH4g and PE wax graft PVC-g-PEW4g, inorganic assistant is calcium oxide and bicarbonate
The equal proportion mixture of sodium.
Accurately weigh zinc-base coordination compound, zinc burns inhibitor, auxiliary heat stabilizer, compatilizer and inorganic assistant, is sequentially added into
In mixer, starting stirring, control rotating speed is 650r/min, is sprayed onto in compound with vaporific by butyl, sprays
Speed is 3.5kg/min, and incorporation time is 3min clock, and then adjusting rotating speed is 150r/min, and mixed on low speed 2.5min clock to obtain final product
Powder body zinc-base composite thermal stabilizer.
Embodiment 7
A kind of powder body zinc-base composite thermal stabilizer, described composite thermal stabilizer is processed from following component: with zinc-base
Thing 40g, zinc burn inhibitor 16g, auxiliary heat stabilizer 13g, compatilizer 6g, inorganic assistant 8g, butyl 6g；Described zinc
Basigamy compound is mixed by following component: zinc acetylacetonate 40g, zinc glycinate 10g, p-tert-butyl benzoic acid zinc 8g and sulfydryl
Acetic acid is against thioesters zinc 5g, and described auxiliary heat stabilizer is methyl-silicone oil 6.5g and hydrazino benzyl formate 6.5g composition, and zinc burns suppression
Agent is by tetramethylolmethane two p-tert-butyl benzoic acid ester, sodium citrate and the coordination compound of 4A molecular sieve 1:5:3 in mass ratio, compatilizer
For maleic anhydride monomer graft PVC-g-MAH3g and PE wax graft PVC-g-PEW3g, inorganic assistant is attapulgite and carbon
The equal proportion mixture of acid hydrogen sodium.
Accurately weigh zinc-base coordination compound, zinc burns inhibitor, auxiliary heat stabilizer, compatilizer and inorganic assistant, is sequentially added into
In mixer, starting stirring, control rotating speed is 550r/min, is sprayed onto in compound with vaporific by butyl, sprays
Speed is 3kg/min, and incorporation time is 3.5min clock, and then adjusting rotating speed is 250r/min, and mixed on low speed 1.5min clock to obtain final product
Powder body zinc-base composite thermal stabilizer.
Embodiment 8
A kind of powder body zinc-base composite thermal stabilizer, described composite thermal stabilizer is processed from following component: with zinc-base
Thing 48g, zinc burn inhibitor 16g, auxiliary heat stabilizer 20g, compatilizer 8g, inorganic assistant 12g, butyl 8g；Described
Zinc-base coordination compound is mixed by following component: zinc acetylacetonate 43g, zinc glycinate 12g, p-tert-butyl benzoic acid zinc 8g and mercapto
Guanidine-acetic acid is against thioesters zinc 6g, and described auxiliary heat stabilizer is methyl-silicone oil 10g and hydrazino benzyl formate 10g composition, and zinc burns suppression
Agent is by tetramethylolmethane two p-tert-butyl benzoic acid ester, sodium citrate and the coordination compound of 4A molecular sieve 1:2:3 in mass ratio, compatilizer
For maleic anhydride monomer graft PVC-g-MAH4g and PE wax graft PVC-g-PEW4g, inorganic assistant is attapulgite and carbon
The equal proportion mixture of acid hydrogen sodium.
Accurately weigh zinc-base coordination compound, zinc burns inhibitor, auxiliary heat stabilizer, compatilizer and inorganic assistant, is sequentially added into
In mixer, starting stirring, rotating speed processed is 500r/min, is sprayed onto in compound with vaporific by butyl, sprays speed
Degree is 3.5kg/min, and incorporation time is 2.5min clock, and then adjusting rotating speed is 200r/min, and mixed on low speed 2min clock obtains powder
Body zinc-base composite thermal stabilizer.
Checking example: plate-out is tested
(1) PVC experimental formula:
(a) basic components
Checking example 1-8:PVC (SG-1000, Qilu Co., Ltd., China Petrochemical Corp): 100g, prepared by embodiment 1-8
Powder body zinc-base composite thermal stabilizer: 5g, DOP (Qilu Co., Ltd., China Petrochemical Corp): 35g, red: 1g；
Comparative example: formula, with verifying example, is a difference in that and selects commercially available calcium zinc stabilizer CZ, and consumption is 5g.
(b) white material formula
PVC (SG-1000, Qilu Co., Ltd., China Petrochemical Corp): 100g, Methyltin composite heat stabilizer HTM 2010
(Zhejiang Hai Pudun new material limited company): 1g, DOP (Qilu Co., Ltd., China Petrochemical Corp): 45g, stearic acid (lake
Ling Huxinwang Chemical Co., Ltd. of state city): 0.5g, titanium dioxide (E.I.Du Pont Company): 7g.
(2) prepared by sample:
Sample is accurately weighed, by material mix homogeneously, at 180 ± 2 DEG C, according to basis according to above-mentioned flexible PVC formula
Formula is gone up mixing 10 minutes at opening rubber mixing machine (Hong Yang group), and material is taken off, and white material is added on unwashed roller, mixed
Refine 5 minutes, material is taken off, mixing about 5min, make the PVC coupons of thickness about 1mm, contrast standard red plate progression, result is such as
Shown in table 3.
The pressure analysis degree of table 1 various sample sheet
Table 1 result shows, the pressure analysis degree of powder body zinc-base composite thermal stabilizer of the present invention is significantly less than comparative example, and this is described
The precipitation performance of bright powder body zinc-base composite thermal stabilizer is substantially better than existing calcium zinc stabilizer.
Checking example: bloom is tested
(1) experimental formula: PVC (SG-1000, Qilu Co., Ltd., China Petrochemical Corp): 100g, DOP:50g, embodiment
Powder body zinc-base composite thermal stabilizer prepared by 1-8: 5g.
Comparative example: formula, with verifying example, is a difference in that and selects commercially available calcium zinc stabilizer CZ, and consumption is 5g.
(2) prepared by sample: by (1) formula by dispensing mix homogeneously, plasticate on 160 DEG C of rubber mixing machines 5min, then with flat
Plate vulcanizer is made 40mm × 40mm × 1mm and is tested blackboard.
(3) bloom test: test plate (panel) is placed in 0.5% calcium chloride water of 60 DEG C until spraying whiteness and not being further added by.Will
Test blackboard carries out spraying whiteness and compares with standard blackboard, i.e. can determine that the bloom degree of stabilizer.The results are shown in Table 2.
The bloom degree of table 2 various sample sheet
Table 2 result shows, the powder body zinc-base composite thermal stabilizer bloom degree of the present invention is significantly less than comparative example, and this is described
Bright powder body zinc-base composite thermal stabilizer bloom performance is substantially better than existing calcium zinc stabilizer.
Checking example: stability experiment
(1) according to formula (being shown in Table 3) precise PVC compound, the static and test of Congo red time is carried out.
Table 3 test recipe
| Auxiliary agent | Formula |
| PVC | 100 |
| DOP | 50 |
| Stabilizer | 5 |
| Fine particle calcium carbonate (Himpton) | 50 |
| ESBO | 5 |
| OPE | 0.5 |
| Stearic acid | 0.5 |
Comparative example: formula, with table 3, is a difference in that and selects commercially available calcium zinc stabilizer CZ, and consumption is 5g.
(2) Congo red timing: made checking example 1-8 print and comparative example print are all cut into 4mm × 4mm ×
1mm sheet is loaded in the test tube of 150mm × 15mm, is rolled into by Congored test paper and ring-type puts into test tube mouth, with clean silica gel plug
Stopper.Inserting in the baffle holes on constant temperature glycerol bath, keeping sample upper end is 20mm from glycerol upper end elevation of water, oil bath
It is 200 DEG C, is as the criterion with mercurial thermometer.Starting timing, Congored test paper lower end starts to become the blue used time when being Congo red
Between, corresponding initial stage thermal stability, experimental result is shown in Table 4.
(3) static heat stabilization time: ageing oven temperature is set to 185 DEG C, checking example 1-8 print and comparative example print are put
In baking oven, the test piece blackening time is static heat stabilization time, corresponding long-term thermal stability performance, experimental result Fig. 1.
It will be seen from figure 1 that powder body zinc-base composite thermal stabilizer Congo red time of preparing of the present invention and static heat are stable
Time is substantially better than comparative example commercially available calcium zinc stabilizer products C Z, and the zinc-base stabilizer product similar with market that the present invention prepares is described
Condition ratio, has more preferable initial stage, long-time stability and anti-yellowing property.Embodiment described above is the one of the present invention
Preferably scheme, not makees any pro forma restriction, without departing from the technical scheme described in claim to the present invention
Other variant and remodeling is also had under premise.
Claims (9)
1. a powder body zinc-base composite thermal stabilizer, it is characterised in that: described composite thermal stabilizer is by the component of following weight portion
Process:
Zinc-base coordination compound 35-55 part
Zinc burns inhibitor 10-20 part
Auxiliary heat stabilizer 10-20 part
Compatilizer 5-10 part
Inorganic assistant 5-15 part
Butyl 5-10 part；
Described zinc-base coordination compound is that zinc acetylacetonate, zinc glycinate, p-tert-butyl benzoic acid zinc and TGA are against thioesters zinc
Compositions, described auxiliary heat stabilizer is appointing in three (glycidyl) chlorinated isocyanurates, methyl-silicone oil and hydrazino benzyl formate
Anticipate the arbitrary proportion mixture of two kinds.
Powder body zinc-base composite thermal stabilizer the most according to claim 1, it is characterised in that: described composite thermal stabilizer by under
The component of row weight portion processes:
Zinc-base coordination compound 40-50 part
Zinc burns inhibitor 15-20 part
Auxiliary heat stabilizer 10-15 part
Compatilizer 5-8 part
Inorganic assistant 5-10 part
Butyl 5-8 part.
Powder body zinc-base composite thermal stabilizer the most according to claim 1, it is characterised in that: described composite thermal stabilizer by under
The component of row weight portion processes:
Zinc-base coordination compound 45 parts
Zinc burns inhibitor 18 parts
Auxiliary heat stabilizer 14 parts
Compatilizer 7.5 parts
Inorganic assistant 8 parts
Butyl 7 parts.
4. according to the powder body zinc-base composite thermal stabilizer described in claim 1 or 2 or 3, it is characterised in that: described zinc-base coordination compound
Weight portion consist of: zinc acetylacetonate 30-45 part, zinc glycinate 5-15 part, p-tert-butyl benzoic acid zinc 3-10 part, sulfydryl second
The inverse thioesters zinc 2-8 part of acid.
5. according to the powder body zinc-base composite thermal stabilizer described in claim 1 or 2 or 3, it is characterised in that: described zinc burns inhibitor
For tetramethylolmethane two p-tert-butyl benzoic acid ester, sodium citrate and 4A molecular sieve 1:(2 in mass ratio～5): the cooperation of (3～5)
Thing.
6. according to the powder body zinc-base composite thermal stabilizer described in claim 1 or 2 or 3, it is characterised in that: described compatilizer is horse
Come in anhydride monomers graft PVC-g-MAH and PE wax graft PVC-g-PEW any one, or the arbitrary proportion of two kinds
Mixture.
7. according to the powder body zinc-base composite thermal stabilizer described in claim 1 or 2 or 3, it is characterised in that: described inorganic assistant is
The arbitrary proportion mixture of any two kinds in attapulgite, calcium oxide and sodium bicarbonate.
8. the preparation method of the powder body zinc-base composite thermal stabilizer described in a claim 1-7 any one, it is characterised in that:
Described method is carried out as follows:
(1) high velocity fog mix stages: by the zinc-base coordination compound of formula ratio, zinc burn inhibitor, auxiliary heat stabilizer, compatilizer and
Inorganic assistant is sequentially added in mixer, starts stirring, and control rotating speed is 500-650r/min, by butyl with vaporific
Being sprayed onto in compound, spray rate is 2.5-3.5kg/min, and incorporation time is 3-6min clock；
(2) low speed remixes the stage: on the basis of step (1), and adjustment rotating speed is 150-300r/min, mixed on low speed 0.5-
3min clock, obtains powder body zinc-base composite thermal stabilizer.
The preparation method of powder body zinc-base composite thermal stabilizer the most according to claim 8, it is characterised in that: in step (1),
Speed of agitator is 550-600r/min, and butyl spray rate is 3-3.5kg/min, and incorporation time is 3-5min clock；
In step (2), speed of agitator is 200-300r/min, and incorporation time is 1-3min clock.
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| CN110655680A (en) * | 2019-10-18 | 2020-01-07 | 浙江传化华洋化工有限公司 | Mixed anion zinc monomer, and composition and application thereof |
| CN110964272A (en) * | 2019-12-18 | 2020-04-07 | 惠州市兴邦新材料科技有限公司 | Zinc burning inhibitor for PVC (polyvinyl chloride) and preparation method thereof |
| CN115216062A (en) * | 2022-07-29 | 2022-10-21 | 青岛厚德天圆创新科技有限公司 | Production process of zinc burning inhibitor, product and application thereof |
| CN115449127A (en) * | 2022-09-02 | 2022-12-09 | 浙江工业大学 | Dianion type zinc salt heat stabilizer for transparent PVC and preparation method and application thereof |
| CN115505171A (en) * | 2022-09-27 | 2022-12-23 | 浙江工业大学 | Novel organic zinc salt PVC compound heat stabilizer and preparation method and application thereof |
| CN115558163A (en) * | 2022-11-17 | 2023-01-03 | 山东东临新材料股份有限公司 | Preparation method of composite heat stabilizer containing tris (glycidyl) isocyanurate |
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| CN110655680A (en) * | 2019-10-18 | 2020-01-07 | 浙江传化华洋化工有限公司 | Mixed anion zinc monomer, and composition and application thereof |
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| CN110964272A (en) * | 2019-12-18 | 2020-04-07 | 惠州市兴邦新材料科技有限公司 | Zinc burning inhibitor for PVC (polyvinyl chloride) and preparation method thereof |
| CN115216062A (en) * | 2022-07-29 | 2022-10-21 | 青岛厚德天圆创新科技有限公司 | Production process of zinc burning inhibitor, product and application thereof |
| CN115449127A (en) * | 2022-09-02 | 2022-12-09 | 浙江工业大学 | Dianion type zinc salt heat stabilizer for transparent PVC and preparation method and application thereof |
| CN115449127B (en) * | 2022-09-02 | 2024-01-12 | 浙江工业大学 | Double-anion zinc salt heat stabilizer for transparent PVC, and preparation method and application thereof |
| CN115505171A (en) * | 2022-09-27 | 2022-12-23 | 浙江工业大学 | Novel organic zinc salt PVC compound heat stabilizer and preparation method and application thereof |
| CN115505171B (en) * | 2022-09-27 | 2023-09-05 | 浙江工业大学 | Novel organic zinc salt PVC compound heat stabilizer and preparation method and application thereof |
| CN115558163A (en) * | 2022-11-17 | 2023-01-03 | 山东东临新材料股份有限公司 | Preparation method of composite heat stabilizer containing tris (glycidyl) isocyanurate |
| CN115558163B (en) * | 2022-11-17 | 2023-03-24 | 山东东临新材料股份有限公司 | Preparation method of composite heat stabilizer containing tris (glycidyl) isocyanurate |
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Application publication date: 20161207 |