CN105315574B - A kind of PVC calcium zinc heat stabilizers and its application - Google Patents
A kind of PVC calcium zinc heat stabilizers and its application Download PDFInfo
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Abstract
A kind of PVC calcium zinc heat stabilizers of present invention offer and its application, the calcium zinc heat stabilizer are made of 50-80 parts of main stabilizers and 20-50 parts of auxiliary stabilizers；The main stabilizer is made of 10-50 parts of quinolone zinc salts and 10-70 parts of quinolone calcium salts；The auxiliary stabilizer is a kind of compound of the arbitrary proportion of the or two of which in triphenyl phosphite, epoxidized soybean oil, octyl epoxy stearate, pentaerythrite, dipentaerythritol, D-sorbite, trimethylolpropane, dibenzoyl methane, stearoyl benzoyl methane, uracil or more；PVC of the present invention not only has good PVC thermal stabilities with calcium zinc heat stabilizer, while having the function of preferable antibacterial surface.
Description
(1) technical field
The present invention relates to polyvinyl chloride (PVC) heat stabilizer fields, especially have both the environmentally friendly, efficient of antibacterial functions
PVC calcium zinc heat stabilizers and its preparation and application.
(2) background technology
Polyvinyl chloride (PVC) is as one of five big resins for universal use (PE, PP, PVC, PS, ABS), the quilt in worldwide
It is widely used, nowadays its yield is only second to polyethylene.Polyvinyl chloride relies on its cheap and excellent characteristic, such as acid and alkali-resistance corruption
Erosion, high mechanical strength, it is fire-retardant the features such as be widely used in various fields, as the film of industrial and agricultural production, infusion bag medically,
Tubing, proximate matter etc..But since polyvinyl chloride is at 140 DEG C, chlorine atom thereon will be removed with neighbouring hydrogen atom
Reaction generates HCl and double bond, and the hydrogen chloride generated has autocatalysis, promotes the removing of other chlorine atoms, at PVC points
Conjugated double bond is generated in subchain, and the chemical reactions such as degradation, crosslinking further occur, cause PVC product to darken, mechanical property
It is deteriorated.And the processing temperature of PVC is higher than its decomposition temperature at 160-180 DEG C.Therefore, in PVC process, it is necessary to add
The processing aids such as heat stabilizer, prevent PVC from degrading in process, lead to not use.Heat stabilizer for PVC type
It is various, mainly there are lead salts, metal soap (mainly calcium zinc salt), organic tin, organic heat stabilizers class.But the mankind are to environment
The concern of safety and health proposes the higher requirement such as safe and environment-friendly to heat stabilizer for PVC, and various countries also put into effect phase
Pass policy is forbidden to use the heat stabilizer for PVC (lead salts) containing heavy metal.Organic tin heat stabilizer effect is preferable, but its valence
Lattice are expensive, and part heat stabilizer is toxic, it is thus impossible to be widely used.Organic type thermal stabilizing agent research is more popular, but at present
Result of study show that its thermostable effect can't compare favourably with existing commercialized heat stabilizer.Metal soap thermostabilization
Agent, especially calcium zinc heat stabilizer, it is nontoxic, environmentally friendly, moderate, stablizing effect is good due to its advantages that, be increasingly becoming heat
Main product in stabilizer.But current calcium zinc heat stabilizer is mainly calcium stearate/zinc stearate heat stabilizer system,
Anion stearic acid does not have the functions such as absorbing hydrogen chloride, has primarily served lubricating action, therefore, it is necessary to other auxiliary stabilizers
Collaboration uses, and improves stability.In order to improve the thermostable effect of calcium zinc heat stabilizer, developed using other carboxylic-acid substances
Novel, efficient, environmentally friendly calcium zinc heat stabilizer is the research hotspot of current heat stabilizer.
Based on the organic additive of essence and its addition that PVC is hydrocarbon, the surface of product is easier to grow various
Bacterium, this is also limitation PVC an important factor for the fields such as drinking-water pipe use.In order to solve this problem, it generally requires
The antiseptic of organic or inorganic is added in PVC product.If the necessary additive of PVC has antibacterial functions, need not additionally add
Add antiseptic, contributes to the production cost for reducing PVC product, reduce PVC auxiliary agent types, simplify formula, avoid between auxiliary agent
Side reaction.Therefore, environmentally friendly, the efficient heat stabilizer for PVC that exploitation has both antibacterial functions has good market prospects.
(3) invention content
The present invention provides a kind of PVC calcium zinc heat stabilizers, not only have good PVC thermal stabilities, simultaneously
Has the function of preferable antibacterial surface, thus in the case where adding a kind of auxiliary agent, the PVC product of preparation has been provided simultaneously with hot steady
Fixed and two big function of antibacterial, improves product quality, reduces the cost of antibacterial PVC product, simplifies antibacterial PVC formulas.
Specific technical solution of the present invention is as follows：
The present invention provides a kind of PVC calcium zinc heat stabilizers, and the PVC calcium zinc heat stabilizers are main steady by 50-80 parts
Determine agent and 20-50 parts of auxiliary stabilizer compositions；The main stabilizer is by 10-50 parts of quinolone zinc salts and 10-70 parts of quinolone calcium
Salt forms；The auxiliary stabilizer is triphenyl phosphite, epoxidized soybean oil, epoxystearic acid (different) monooctyl ester, pentaerythrite, double
One kind in pentaerythrite, D-sorbite, trimethylolpropane, dibenzoyl methane, stearoyl benzoyl methane, uracil or
The mixing of two or more arbitrary proportions.
Further, the preferably described PVC calcium zinc heat stabilizers are by 60-75 parts of main stabilizers and 25-40 parts of auxiliary stabilizers
Composition；The main stabilizer is made of 24-30 parts of quinolone zinc salts and 30-51 parts of quinolone calcium salts.
The triphenyl phosphite molecular formula is C18H15O3P, colourless pale yellow transparent oily liquids are a kind of function admirables
Auxiliary antioxidant, additive flame retardant plasticizer and plastic products anti-aging agent can the effectively photostability of enhanced article and holdings
Its transparency.It is alternatively arranged as the chelating agent in PVC product and stabilizer.
The molecular weight of the epoxidized soybean oil is C57H106O10, it is at normal temperatures light yellow sticky oily liquids, is a kind of
Most popular nontoxic polyvinyl chloride plasticizer and stabilizer.Good with polyvinyl chloride resin compatibility, volatility is low, migration is small.Tool
There are excellent thermal stability and photostability, water resistance and oil resistivity are also good, can assign the good mechanical strength of product, weatherability
And electrical property, and it is non-toxic, it is the chemical technology auxiliary agent for packaging material for food of international endorsement.The product can be used for all
Polrvinyl chloride product.As varieties of food items packaging material, medical product, various films, sheet material, tubing, refrigerator strip of paper used for sealing, artificial leather,
Flooring laminate, plastic wallpaper, electric wire and other daily plastic products etc..
Epoxystearic acid (different) the monooctyl ester molecular formula is C26H50O3, volatility is small, and resistance to extractable and electrical insulating property are good, resistance to
It is cold it is further preferred that, and have preferable heat resistance and the transparency.For the plasticizer and stabilizer of polyvinyl chloride, be suitable for film,
The products such as artificial leather.
The pentaerythrite molecular formula is C5H12O4, white crystals or powder can be used as the stabilizing additive of polyvinyl chloride,
With zinc salt stabilizer and with there is synergistic effect, can replace allyl chloride makes polyvinyl chloride stablize, and can be formed and be complexed with metal
Object.
The dibenzoyl methane C15H12O2, as the co-stabilizer of calcium/zinc hydroxy acid salt stabilising system, there is good association
Same effect.
The stearoyl benzoyl methane molecular formula is C26H42O2, be mainly used as polrvinyl chloride product helps heat stabilizer,
When being cooperateed with main stabilizer Ca/Zn or Ba/Zn in use, coloring early period of product can be reduced and improve later stage heat resistance and transparent
Property, it is usually used in mineral water bottle and other transparent polyvinyl chloride sheet materials, bottle material, membrane product etc..This product is ultraviolet with centainly absorbing
The function of line can provide performance steady in a long-term to product, and nontoxic non-stimulated, can be used for protecting the skin from the anti-of sun burn
Shine frost, face cream.All allow in food packet in the developed countries such as European countries and the U.S., Canada, Australia, Japan
This product is used in dress field.
The uracil molecular formula is C4H4N2O2, white or pale yellow needles crystallization, 338 DEG C of fusing point is soluble in hot water,
It is dissolved in weak aqua ammonia, is slightly soluble in cold water, does not dissolve in ethyl alcohol and ether.
The synthesis route of quinolone zinc salt or quinolone calcium salt in main stabilizer of the present invention is as shown in Figure 1, tool
Preparation carries out as follows：Carbostyril compound shown in formula (I) is weighed, and solvent is added, in room temperature (25
DEG C) be uniformly mixed under the conditions of -60 DEG C, it is added alkali, 25 DEG C -60 DEG C the reaction was continued 0.5-2h add zinc salt or calcium salt, 25 DEG C -
60 DEG C of the reaction was continued 4-12h, filtering, without zinc ion or calcium ion, 30- in Washing of Filter Cake (preferably 70 DEG C of hot water washings) to filtrate
Dry 12-48h, obtains quinolone zinc salt or quinolone calcium salt respectively under 50 DEG C of vacuum conditions；
In formula (I), R1For H or F；R2For H, CH3, R3For C2H5,R4For H, F, Cl or OCH3；Or R3、R4Connection cyclization；X1For CH or N；X2For N or C；
X3For N or C；
The solvent is water or methanol, and the solvent volume dosage is in terms of carbostyril compound quality shown in formula (I)
For 50~77ml/g；The alkali is sodium hydroxide, ammonium hydroxide, sodium bicarbonate or sodium carbonate, quinolones shown in the formula (I)
It is 1 to close the ratio between amount of substance of object and alkali:1.5-2；The calcium salt is calcium chloride or perchlorate hexahydrate's calcium；The zinc salt is acetic acid
Zinc, zinc sulfate, perchlorate hexahydrate's zinc or zinc chloride, carbostyril compound shown in the formula (I) feed intake with calcium salt and zinc salt
The ratio between amount of substance is 1:0.5-1.5.
Further, carbostyril compound shown in the formula (I) is shown in pipemidic acid, formula (III) shown in formula (II)
Orfloxacin, oxolinic acid shown in cinoxacin or formula (V) shown in formula (IV)；
Quinolone calcium salt of the present invention is orfloxacin calcium, formula shown in pipemidic acid calcium, formula (VII) shown in formula (VI)
(VIII) oxolinic acid calcium shown in cinoxacin calcium shown in or formula (IX), the quinolone zinc salt are pyrrole piperazine shown in formula (X)
Oxolinic acid zinc shown in cinoxacin zinc or formula (XIII) shown in Zinc Norfloxacin, formula (XII) shown in sour zinc, formula (XI)；
Further, the main stabilizer is the mixture of 30-48 parts of Zn-PPAs and 12-30 parts of pipemidic acid calcium, Huo Zhewei
The mixture of 14-20 parts of cinoxacin zinc and 30-56 parts of cinoxacin calcium.
Auxiliary stabilizer of the present invention is one of the mixture of following weight proportion：(1) 8 parts of dibenzoyl methane, season
Penta 8 parts of tetrol, 24 parts of triphenyl phosphite；(2) 15 parts of dibenzoyl methane, 25 parts of pentaerythrite, 10 parts of uracil；(3) two
10 parts of benzoyl methane, 8 parts of pentaerythrite, 32 parts of triphenyl phosphite；(4) 10 parts of dibenzoyl methane, triphenyl phosphite
30 parts；(5) 10 parts of dibenzoyl methane, 20 parts of triphenyl phosphite；(6) 10 parts of dibenzoyl methane, 10 parts of pentaerythrite, urine
10 parts of pyrimidine；(7) 10 parts of uracil, 30 parts of triphenyl phosphite；(8) 10 parts of dibenzoyl methane, 10 parts of pentaerythrite, phosphorous
20 parts of triphenyl phosphate ester.
Further, PVC calcium zinc heat stabilizers of the present invention by 20-48 parts of quinolone zinc, 12-30 parts of quinolone calcium,
8-10 parts of dibenzoyl methanes, 8-10 parts of pentaerythrites, 20-32 parts of triphenyl phosphite compositions.
Further, PVC calcium zinc heat stabilizers of the present invention by 14-15 parts of quinolone zinc, 35-56 parts of quinolone calcium,
10-15 parts of dibenzoyl methanes, 10-25 parts of pentaerythrites, 10 parts of uracil compositions.
Further, PVC calcium zinc heat stabilizers of the present invention by 14-48 parts of quinolone zinc, 12-56 parts of quinolone calcium,
10 parts of dibenzoyl methanes, 20-30 parts of triphenyl phosphite compositions.
Further, the PVC with calcium zinc heat stabilizer preferably by 30 parts of Zn-PPAs, 30 parts of pipemidic acid calcium, 8 parts of hexichol first
Acyl methane, 8 parts of pentaerythrites, 24 portions of triphenyl phosphites mix 10min using high-speed mixer high speed (2250rpm), obtain
Heat stabilizer mixture.
Further, the PVC with calcium zinc heat stabilizer preferably by 20 parts of cinoxacin zinc salts, 30 parts of cinoxacin calcium salts,
10 parts of dibenzoyl methanes, 8 parts of pentaerythrites, 32 parts of triphenyl phosphite compositions.
Further, the preferably described PVC calcium zinc heat stabilizers are by 17.4 parts of oxolinic acid zinc, 62.6 parts of oxolinic acid calcium, 20 parts
Dibenzoyl methane forms.
The preparation method of PVC of the present invention calcium zinc heat stabilizers is：High speed is added after the raw material of formula ratio is mixed
Mixing machine, high speed (2250rpm) mix 10min, obtain PVC calcium zinc heat stabilizers.
The invention further relates to application of the PVC calcium zinc heat stabilizers in preparing antibacterial PVC material, wherein described
Antibacterial PVC material includes 2-8 parts of PVC calcium zinc heat stabilizers and 92-98 parts of PVC.
After the mechanical mixtures such as PVC calcium zinc heat stabilizers of the present invention and PVC powder, other auxiliary agents, filler, using double
The process equipments such as roller open mill, extruder, mixer prepare PVC sample.
The present invention has the following advantages：1. quinolone is pharmaceutical intermediate, the quinolone calcium salt synthesized, quinolone zinc
Salt is nontoxic, environmentally friendly, meets heat stabilizer for PVC development trend；2. quinolone calcium zinc heat stabilizer had both had good PVC heat steady
Determine effect, for example, when 4 parts of addition oxolinic acid calcium zinc stabilizer system, Congo red stabilization time reaches 143min, baking oven steady stability
Time is 250min, and the torque dynamic stability time is up to 38min, and the PVC product prepared has antibacterial functions, reaches antibacterium
II grade of performance.Therefore, tubing, daily necessities, infant article can be preferably applied to using the PVC product of heat stabilizer of the present invention
Etc. the field for needing antibacterial.3. the long-time stability of the heat stabilizer for PVC of the present invention are better than commercialized zinc stearate/tristearin
Sour calcium heat stabilizer has good market application prospect.(4) it illustrates
Fig. 1 is the synthesis route of quinolone zinc salt or quinolone calcium salt in main stabilizer of the present invention.
(5) specific implementation mode
Technical scheme of the present invention is further described in detail below by embodiment, but protection scope of the present invention is not
It is limited to this.
The preparation of 1 pipemidic acid calcium of embodiment
3.033g (8.5mmol) pipemidic acids and 150mL water are uniformly mixed at 45 DEG C of room temperature, 0.6g (15mmol) is added
In 250mL flasks, 50 DEG C of reaction 2h generate pipemidic acid sodium salt, then add 1.11g (10mmol) calcium chloride sodium hydroxide
Into flask, it is stirred to react 12h at 60 DEG C, generates precipitation, reaction solution is used into filtered on buchner funnel, 70 DEG C of hot water of filter cake
Without chlorion in washing to cleaning solution, it is placed in drying in 30 DEG C of vacuum drying ovens and for 24 hours, obtains pipemidic acid calcium 3.1g.
The metals such as calcium, zinc member is measured using Xray fluorescence spectrometer (ARL ADVANT ' X, Thermo fisher, USA)
Element and fluorine element measure carbon, hydrogen, nitrogen member using organic element analyzer (vario Macro cube, Elementar, Germany)
Cellulose content.
Elemental analysis result：6% calcium；52% carbon；22% nitrogen；5% hydrogen.
2 Zn-PPA of embodiment
3.033g pipemidic acids (8.5mmol) are uniformly mixed with 150mL water at 45 DEG C, 0.6g (15mmol) hydrogen-oxygen is added
Change sodium in 250mL flasks, 40 DEG C of reaction 1h generate pipemidic acid sodium salt, then add 2.745g (15mmol) zinc acetate and arrive
In flask, continue to be stirred to react 4h, generate precipitation, reaction solution is used into filtered on buchner funnel, filter cake with 70 DEG C of hot water wash to
Without acetate ion in cleaning solution, is dried in 40 DEG C of vacuum drying ovens for 24 hours, obtain Zn-PPA 2.9g.
Element test method is the same as embodiment 1.
Elemental analysis result：10% zinc；50% carbon；20% nitrogen；6% hydrogen.
3 Zinc Norfloxacin of embodiment
By 3.192g (10mmol) orfloxacins be uniformly mixed at 60 DEG C in 190mL distilled water, be added 2.12g
(20mmol) sodium carbonate reacts 2h at 30 DEG C, and 1.45g (9mmol) zinc sulfate is added, and is stirred to react 6h, generates precipitation, will be anti-
Answer liquid that filtered on buchner funnel, filter cake is used to wash into cleaning solution sulfate radical-free ion, 50 DEG C of vacuum drying with 70 DEG C of hot water
12h obtains Zinc Norfloxacin 3.1g.
Element test method is the same as embodiment 1.
Elemental analysis result：9% zinc；5% fluorine；55% carbon；12% nitrogen；6% hydrogen.
4 orfloxacin calcium of embodiment
3.192g (10mmol) orfloxacins are uniformly mixed with 190mL methanol at 60 DEG C, 2.12g (20mmol) carbon is added
Sour sodium reacts 2h at 30 DEG C, and after 1.11g (10mmol) calcium chloride is added, stirring at normal temperature 12h has precipitation to generate.By reaction solution
Using filtered on buchner funnel, 70 DEG C of hot water of filter cake are washed into cleaning solution without chlorion or calcium ion, in 40 DEG C of vacuum drying ovens
Dry 48h, obtains orfloxacin calcium 2.8g.Element test method is the same as embodiment 1.
Elemental analysis result：6% calcium；5% fluorine；57% carbon；12% nitrogen；5% hydrogen.
5 cinoxacin zinc of embodiment, cinoxacin calcium
2.622g (10mmol) cinoxacins are uniformly mixed with 190mL methanol at 50 DEG C, 0.6g (20mmol) is added
Sodium hydroxide, 35 DEG C of stirring 0.5h.2.745g (15mmol) zinc acetate is added, 25 DEG C of stirring 12h of room temperature generate precipitation, will
Reaction solution uses filtered on buchner funnel, and filter cake is washed into cleaning solution with 70 DEG C of hot water without no acetate ion, then at 40 DEG C
Dry 48h, obtains cinoxacin zinc 2.5g in vacuum drying oven.
Cinoxacin calcium preparation method is changed to 1.11g calcium chloride with cinoxacin zinc, by 2.745g zinc acetates, obtains western promise
Husky star calcium 2.4g.
Element test method is the same as embodiment 1.
Cinoxacin Zn-ef ficiency analysis result：11% zinc；49% carbon；10% nitrogen；3% hydrogen.
Cinoxacin calcium constituent analysis result：7% calcium；51% carbon；10% nitrogen；4% hydrogen.
6 oxolinic acid zinc of embodiment, oxolinic acid calcium
The preparation method of oxolinic acid zinc carries out as follows：2.613g (10mmol) oxolinic acids and 200mL methanol are existed
It is uniformly mixed under room temperature (25 DEG C), 2.12g (20mmol) sodium carbonate is added, reacts 1h at 40 DEG C.Add 2.68g
(7mmol) zinc perchlorate, stirring at normal temperature 8h generate precipitation, reaction solution are filtered, filter cake is washed with 70 DEG C of hot water into cleaning solution
Without perchlorate, then drying for 24 hours, obtains oxolinic acid zinc 2.5g in 50 DEG C of vacuum drying ovens.
The preparation method of oxolinic acid calcium is changed to 2.43g Calcium perchlorates with oxolinic acid zinc, by 2.68g zinc perchlorates, is disliked
Quinoline acid calcium 2.6g.
Element test method is the same as embodiment 1.
Oxolinic acid Zn-ef ficiency analysis result：11% zinc；53% carbon；5% nitrogen；4% hydrogen.
Oxolinic acid calcium constituent analysis result：7% calcium；56% carbon；5% nitrogen；4% hydrogen.
Embodiment 7
(1) PVC calcium zinc heat stabilizer formulation by weight：30g Zn-PPAs, 30g pipemidic acid calcium, 8g dibenzoyl methanes,
8g pentaerythrites, 24g triphenyl phosphites.
(2) PVC calcium zinc heat stabilizer preparation methods：High-speed mixer (model GH- is added in the raw material of formula ratio
10DY, Beijing Ying Te plastics machineries factory of producer), the mixed at high speed 10min at 2250rpm obtains PVC calcium zinc heat stabilizers.
(3) PVC sample quality formula is：PVC calcium zinc stabilizers:DOP:PVC=2:50:100, specifically by step
(2) prepare 2g calcium zinc heat stabilizers and 50g DOP (plasticizer phthalic acid dioctyl ester) and 100g PVC (polyvinyl chloride,
SG5 types) 180 DEG C are placed in, rotating speed is in the two-roll mill of 11rpm, and after being kneaded 5min, regulating roller spacing obtains thickness about 1mm
PVC sheet, be used for heat stability testing.
According to GB/T 2917.1-2002, GB/T 9349-2002, ASTM D 2538-02, QB/T2591-2003 difference
Test Congo red stabilization time, baking oven steady stability time, torque rheometer dynamic stability time and anti-microbial property.
Test result：Congo red stabilization time：81min；Baking oven steady stability time 180min；When torque dynamic stability
Between：35min；Antibacterium test result：Bacteria resistance can be II grade.
Comparative example 1
Heat stabilizer for PVC formula：20g zinc stearates, 80g calcium stearates.
PVC sample quality formula is：Heat stabilizer for PVC:DOP:PVC=4:30:100.Other operations are the same as embodiment 7.
Test result：Congo red stabilization time：28min；The baking oven steady stability time：110min；When torque dynamic stability
Between：12min；Antibacterium test result：Off grade.
Comparative example 2
PVC is formulated with calcium zinc heat stabilizer：20g Zinc Norfloxacins, 80g orfloxacin calcium.
PVC sample quality formula is：PVC calcium zinc stabilizers:DOP:PVC=4:30:100.Other same embodiments of operation
7。
Test result：Congo red stabilization time：40min；The baking oven steady stability time：180min；When torque dynamic stability
Between：13min；Antibacterium test result：Bacteria resistance can be II grade.
Embodiment 8
PVC is formulated with calcium zinc heat stabilizer：48g Zn-PPAs, 12g pipemidic acid calcium, 10g dibenzoyl methanes, 30g phosphorous
Triphenyl phosphate ester.
PVC sample quality formula is：PVC calcium zinc stabilizers:DOP:PVC=3:50:100.Other same embodiments of operation
7。
Test result：Congo red stabilization time：117min；The baking oven steady stability time：220min；When torque dynamic stability
Between：39min；Antibacterium test result：Bacteria resistance can be II grade.
Embodiment 9
PVC is formulated with calcium zinc heat stabilizer：15g Zn-PPAs, 35g pipemidic acid calcium, 15g dibenzoyl methanes, 25g seasons penta
Tetrol, 10g uracils.
PVC sample quality formula is：PVC calcium zinc stabilizers:DOP:PVC=4:50:100.Other same embodiments of operation
7。
Test result：Congo red stabilization time：145min；The baking oven steady stability time：260min；When torque dynamic stability
Between：46min；Antibacterium test result：Bacteria resistance can be II grade.
Embodiment 10
PVC is formulated with calcium zinc heat stabilizer：20g cinoxacin zinc salts, 30g cinoxacin calcium salts, 10g dibenzoyl first
Alkane, 8g pentaerythrites, 32g triphenyl phosphites.
PVC sample quality formula is：PVC calcium zinc stabilizers:DOP:PVC=2:50:100.Other same embodiments of operation
7。
Test result：Congo red stabilization time：75min；The baking oven steady stability time：170min；When torque dynamic stability
Between：33min；Antibacterium test result：Bacteria resistance can be II grade.
Embodiment 11
PVC is formulated with calcium zinc heat stabilizer：14g cinoxacin zinc, 56g cinoxacin calcium, 10g dibenzoyl methanes, 20g
Triphenyl phosphite.
PVC sample formula is：PVC calcium zinc stabilizers:DOP:PVC=2:50:100.Other operations are the same as embodiment 7.
Test result：Congo red stabilization time：79min；The baking oven steady stability time：190min；When torque dynamic stability
Between：35min；Antibacterium test result：Bacteria resistance can be II grade.
Embodiment 12
PVC is formulated with calcium zinc heat stabilizer：14g Zinc Norfloxacins, 56g orfloxacin calcium, 10g dibenzoyl methanes, 10g seasons penta
Tetrol, 10g uracils.
PVC sample formula is：PVC calcium zinc stabilizers:DOP:PVC=4:50:100.Other operations are the same as embodiment 7.
Test result：Congo red stabilization time：138min；The baking oven steady stability time：230min；When torque dynamic stability
Between：43min；Antibacterium test result：Bacteria resistance can be II grade.
Embodiment 13
PVC is formulated with calcium zinc heat stabilizer：40g Zinc Norfloxacins, 20g orfloxacin calcium, 10g uracils, 30g phosphorous triphenyl phosphates
Ester.
PVC sample formula is：PVC calcium zinc stabilizers:DOP:PVC=4:50:100.Other operations are the same as embodiment 7.
Test result：Congo red stabilization time：107min；The baking oven steady stability time：210min；When torque dynamic stability
Between：39min；Antibacterium test result：Bacteria resistance can be II grade.
Embodiment 14
PVC is formulated with calcium zinc heat stabilizer：17.4g oxolinic acid zinc, 62.6g oxolinic acid calcium, 20g dibenzoyl methanes.
PVC sample formula is：PVC calcium zinc stabilizers:DOP:PVC=4:50:100.Other operations are the same as embodiment 7.
Test result：Congo red stabilization time：143min；The baking oven steady stability time：250min；When torque dynamic stability
Between：38min；Antibacterium test result：Bacteria resistance can be II grade.
Embodiment 15
PVC is formulated with calcium zinc heat stabilizer：48g oxolinic acid zinc, 12g oxolinic acid calcium, 10g dibenzoyl methanes, 10g seasons penta
Tetrol, 20g triphenyl phosphites.
PVC sample formula is：PVC calcium zinc stabilizers:DOP:PVC=2:50:100.Other operations are the same as embodiment 7.
Test result：Congo red stabilization time：76min；The baking oven steady stability time：140min；When torque dynamic stability
Between：26min；Antibacterium test result：Bacteria resistance can be II grade.
Claims (9)
1. a kind of PVC calcium zinc heat stabilizers, it is characterised in that the calcium zinc heat stabilizer is by 50-80 parts of main stabilizers and 20-
50 parts of auxiliary stabilizer compositions；The main stabilizer is made of 10-50 parts of quinolone zinc salts and 10-70 parts of quinolone calcium salts；Institute
It is that one or more of triphenyl phosphite, pentaerythrite, dibenzoyl methane, uracil are arbitrary to state auxiliary stabilizer
The mixing of ratio；The quinolone calcium salt is orfloxacin calcium or formula (IX) shown in pipemidic acid calcium, formula (VII) shown in formula (VI)
Shown in oxolinic acid calcium, the quinolone zinc salt is Zn-PPA, Zinc Norfloxacin or formula shown in formula (XI) shown in formula (X)
(XIII) oxolinic acid zinc shown in；
2. PVC calcium zinc heat stabilizers as described in claim 1, it is characterised in that the PVC calcium zinc heat stabilizers are by 60-
75 parts of main stabilizers and 25-40 parts of auxiliary stabilizer compositions；The main stabilizer is by 24-30 parts of quinolone zinc salts and 30-51 parts
Quinolone calcium salt forms.
3. PVC calcium zinc heat stabilizers as described in claim 1, it is characterised in that in the main stabilizer quinolone zinc salt or
The preparation method of quinolone calcium salt carries out as follows：Carbostyril compound shown in formula (I) is weighed, and solvent is added,
It is uniformly mixed under the conditions of 25-60 DEG C, is added alkali, 25-60 DEG C of the reaction was continued 0.5-2h adds zinc salt or calcium salt, 25-60 DEG C
The reaction was continued 4-12h, filtering, without zinc ion or calcium ion in Washing of Filter Cake to filtrate, dry 12- under 30-50 DEG C of vacuum condition
48h obtains quinolone zinc salt or quinolone calcium salt；
In formula (I), R1For H or F；R2For H, CH3, R3For C2H5,R4For H, F, Cl or OCH3；Or R3、R4Connection cyclization；X1For CH or N；X2For N or C；
X3For N or C；
The solvent is water or methanol, and the volumetric usage of the solvent is calculated as with carbostyril compound quality shown in formula (I)
50~77ml/g；The alkali is sodium hydroxide, ammonium hydroxide, sodium bicarbonate or sodium carbonate, quinolones chemical combination shown in the formula (I)
The ratio between amount of substance of object and alkali is 1:1.5-2；The calcium salt is calcium chloride or Calcium perchlorate, and the zinc salt is zinc acetate, sulphur
Sour zinc, zinc perchlorate or zinc chloride；Carbostyril compound shown in the formula (I) and calcium salt and zinc salt feed intake substance amount it
Than being 1:0.5-1.5.
4. PVC calcium zinc heat stabilizers as claimed in claim 3, it is characterised in that the main stabilizer is 30-48 parts of pyrrole piperazines
The mixture of sour zinc and 12-30 parts of pipemidic acid calcium.
5. PVC calcium zinc heat stabilizers as described in claim 1, it is characterised in that the auxiliary stabilizer is that following weight is matched
One of the mixture of ratio：(1) 10 parts of dibenzoyl methane, 30 parts of triphenyl phosphite；(2) 10 parts of dibenzoyl methane, season penta
10 parts of tetrol, 10 parts of uracil；(3) 10 parts of uracil, 30 parts of triphenyl phosphite.
6. PVC calcium zinc heat stabilizers as described in claim 1, it is characterised in that the PVC calcium zinc heat stabilizers are by 20-
48 parts of quinolone zinc, 12-30 parts of quinolone calcium, 8-10 parts of dibenzoyl methanes, 8-10 parts of pentaerythrites, 20-32 parts of phosphorous acid
Triphenylmethyl methacrylate forms.
7. PVC calcium zinc heat stabilizers as described in claim 1, which is characterized in that the PVC calcium zinc heat stabilizers are under
Row weight proportion raw material forms：30 parts of Zn-PPAs, 30 parts of pipemidic acid calcium, 8 parts of dibenzoyl methanes, 8 parts of pentaerythrites, 24 parts
Triphenyl phosphite.
8. application of the PVC calcium zinc heat stabilizers as described in claim 1 in preparing antibacterial PVC material.
9. application as claimed in claim 8, it is characterised in that the antibacterial PVC material includes 2-8 parts of PVC calcium zinc thermostabilizations
Agent and 92-98 parts of PVC.
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| CN105713316B (en) * | 2016-02-23 | 2017-11-10 | 东莞市尚诺新材料有限公司 | A kind of transparent no phenol paste shape heat stabilizer and preparation method thereof |
| CN107266443A (en) * | 2017-06-05 | 2017-10-20 | 穆开蕊 | The preparation method of piperidines with PVC stabilizer function and pyridone tin complex |
| CN107266446A (en) * | 2017-06-05 | 2017-10-20 | 毛伸 | The piperidines and the preparation method of pyridone tin complex acted on PVC stabilizer |
| CN107266445A (en) * | 2017-06-05 | 2017-10-20 | 穆开蕊 | The piperidines and the preparation method of the triazole tin complex of pyrido 1,2,3 acted on PVC stabilizer |
| CN107501807B (en) * | 2017-10-09 | 2019-08-27 | 浙江越千树数码科技有限公司 | A kind of cold lamination film having highly resistance Ultraviolet Oxidation performance and anti-microbial property |
| CN107718587B (en) * | 2017-10-23 | 2018-08-14 | 沈坤 | A kind of multifunctional medical conduit and preparation method thereof, application |
| CN108659386A (en) * | 2018-05-04 | 2018-10-16 | 广东祺龙科技有限公司 | A kind of robot drag chain PVC modified materials and preparation method thereof |
| CN111763388A (en) * | 2019-04-02 | 2020-10-13 | 陈立峰 | Powdery calcium-zinc composite heat stabilizer for emulsion-process polyvinyl chloride resin and preparation method thereof |
| CN111233665B (en) * | 2020-03-12 | 2022-05-31 | 山东海螺型材有限责任公司 | Preparation method of zinc metal alkoxide of pentaerythritol ester of p-hydroxybenzoic acid |
| CN111793300A (en) * | 2020-07-09 | 2020-10-20 | 扬州大学 | Soft heat-resisting PVC membrane |
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| CN103374187B (en) * | 2012-04-25 | 2015-12-16 | 吴旅良 | The preparation method of calcium-zinc composite stabilizing agent is produced in one still contiguous segmentation synthesis |
| CN103833739A (en) * | 2014-01-23 | 2014-06-04 | 浙江工业大学 | A calcium-zinc composite heat stabilizer, a preparation method thereof and applications thereof |
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