CN105949508A - Heat stabilizer for PVC (polyvinyl chloride) and preparation method and application thereof - Google Patents
Heat stabilizer for PVC (polyvinyl chloride) and preparation method and application thereof Download PDFInfo
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- CN105949508A CN105949508A CN201610346143.7A CN201610346143A CN105949508A CN 105949508 A CN105949508 A CN 105949508A CN 201610346143 A CN201610346143 A CN 201610346143A CN 105949508 A CN105949508 A CN 105949508A
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Abstract
The invention discloses a heat stabilizer for PVC (polyvinyl chloride) and a preparation method and application thereof. The preparation method includes: subjecting tung maleic anhydride and para aminobenzoic acid to anhydride aminolysis reaction to obtain N-(3-amino-benzoyloxy) tung maleic amic acid; performing one-step reaction of the prepared N-(3-amino-benzoyloxy) tung maleic amic acid and metal oxides or metal hydroxides in solvent to prepare liquid N-(3-amino-benzoyloxy) tung maleic amic acid metal salt; compounding the prepared N-(3-amino-benzoyloxy) tung maleic amic acid calcium salt with zinc salt to obtain a liquid composite heat stabilizer. The prepared calcium-zinc liquid composite heat stabilizer has advantages of nontoxicity, freeness of heavy metals, environment friendliness and the like and endows PVC products with high heat stability and transparency. The preparation method is simple in process route and mild in condition, raw materials which are selected from natural environment-friendly renewable resources are rich in source and low in cost.
Description
Technical field
The invention belongs to plastic additive field, be specifically related to a kind of heat stabilizer for PVC and its preparation method and application.
Background technology
Plastic additive is again plastic additive, such as filler, plasticizer, lubricant, stabilizer, coloring agent etc., is that polymer (closes
Resin) machine-shaping time be its processing characteristics of improvement or by improve the performance of resin own deficiency and some chemical combination that must add
Thing.Therefore, plastic additive occupies the status of particular importance in plastics processing.
Because polrvinyl chloride (PVC) softening temperature differs the least and poor heat stability with decomposition temperature, bring the biggest being stranded to processing
Difficult, it is therefore necessary in its course of processing, to add a certain amount of heat stabilizer to improve its heat stability.In the market conventional
Heat stabilizer, such as lead heat stabilizer, organo-tin het stabilizer etc., product excellent heat stability but its use are increasingly limited
System.Therefore study and develop new calcium zinc heat stabilizer replace or part replace environmentally harmful or higher-priced heat stabilizer (as
Lead salt, barium, cadmium and organotin etc.) have great importance.
Along with the day by day exhausted and environmental pollution of petroleum resources day by day serious in world wide, find high-quality, cheap, renewable
Oil substitute become particularly nervous.China produces nearly 4,000,000 tons of non-edible plant oil per year, containing substantial amounts of unsaturation in oils and fats
Fatty acid, as oleic acid, linoleic acid, linolenic acid etc. can occur many reaction such as sulfonation, aoxidize, hydrogenate, deoxygenate, isomerization,
Polymerization, pyrolysis etc..In this research with tong ma anhydride for development of raw materials one N-(3-amino-benzoic acid base) paulownia horse amic acid calcium zinc again
Closing liquid heat stabilizer, the heat stability significantly improving PVC product gives again its more preferable non-oxidizability and transparency simultaneously.This
From the point of view of invention is in terms of resource selection, material property and production cost three, the most significant.
Summary of the invention
Solve the technical problem that: the present invention is single for existing calcium zinc heat stabilizer product on reply market, it is provided that a kind of PVC
With heat stabilizer and its preparation method and application.
Technical scheme: the preparation method of a kind of heat stabilizer for PVC, is prepared by following steps: the first step: take tong ma anhydride molten
Solution joins in reaction vessel after solvent orange 2 A, is warming up to 25～60 DEG C, by para-amino benzoic acid by with tong ma anhydride in molar ratio
1:1～1.2 is dissolved in solvent orange 2 A, and drops in reaction vessel, isothermal reaction 1～4h after dropping, vacuum drying, obtains
Solid product N-(3-amino-benzoic acid base) paulownia horse amic acid；Solvent orange 2 A used is ethyl acetate, acetone, ethanol and glacial acetic acid
In at least one, twice consumption is respectively tong ma anhydride and 1-20 times of para-amino benzoic acid quality；Second step: by N-(3-
Amino-benzoic acid base) paulownia horse amic acid and solvent B 1:1 in mass ratio～0.3 join in reaction vessel, is warming up to 50～90 DEG C；
Until completely dissolved, by being 0.9～1:1 to be dividedly in some parts metal-oxide with N-(3-amino-benzoic acid base) paulownia horse amic acid mol ratio
Or metal hydroxides, it being warming up to 100～140 DEG C, dropping accounts for N-(3-amino-benzoic acid base) paulownia horse amic acid mass fraction 0.2～1%
Catalyst C, be incubated 2～5h, rotation water is evaporated off, sucking filtration obtains liquid N-(3-amino-benzoic acid base) paulownia horse amic acid slaine；
Described solvent B is at least one in petroleum ether, tasteless kerosene, propylene glycol monomethyl ether, diethylene glycol monobutyl ether；Described burning
Thing is calcium oxide or zinc oxide, and described metal hydroxides is calcium hydroxide, finally gives liquid N-(3-amino-benzoic acid base) paulownia
Horse amic acid metal calcium salt and liquid N-(3-amino-benzoic acid base) paulownia horse amic acid metal zinc salt；Catalyst C is hydrogen peroxide, ice
At least one in acetic acid；3rd step: by prepared liquid N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt and N-(3-amino
-benzoxy) paulownia horse amic acid zinc salt in mass ratio 4～3:1 compounds, and obtains liquid composite thermal stabilizer.
Preferably, above-mentioned solvent orange 2 A is ethyl acetate, and consumption is respectively 1 times of tong ma anhydride quality, para-amino benzoic acid quality
10 times.
Preferably, above-mentioned para-amino benzoic acid is 1:1～1.2 by the mol ratio with tong ma anhydride, and the response time is 4h.
Preferably, above-mentioned solvent B is diethylene glycol monobutyl ether, and consumption is equal with N-(3-amino-benzoic acid base) paulownia horse amic acid quality.
Preferably, above-mentioned metal-oxide is calcium oxide and zinc oxide, consumption be respectively with N-(3-amino-benzoic acid base) paulownia horse acyl
Mol ratio 1:1 of amino acid.
Preferably, above-mentioned catalyst C is glacial acetic acid, accounts for N-(3-amino-benzoic acid base) paulownia horse amic acid mass fraction 0.57%.
Preferably, above-mentioned N-(3-amino-benzoic acid base) paulownia horse amic acid calcium and N-(3-amino-benzoic acid base) paulownia horse amic acid zinc
Mass ratio is 4:1.
The heat stabilizer for PVC that any of the above-described method is prepared.
The heat stabilizer that any of the above-described method is prepared application in preparation PVC product.
Beneficial effect: 1. with Oleum Verniciae fordii as raw material in the present invention, abundant raw material source, product price is cheap, has broken away from oil
The dependence in wage source.
2. compared with the heat stabilizer with common fats acid as basic framework, N-(3-amino-benzoic acid base) the paulownia horse that the present invention prepares
Amic acid slaine introduces multiple functional groups with cooperative effect: contained unsaturated carbon-carbon double bond can be with PVC because of thermal degradation
And the conjugated polyene sequence addition generated, stop it to increase further and shorten conjugated polyene segment, can well suppress product to become
Color；Amide structure contained by Tong Shi can catch chlorine radical, forms acyl chlorides and containing nitrogen free radical, and the latter is again by catching macromole
Hydroperoxyl radical under coming off on chain forms the little molecule containing amino, and this little molecule also has absorption HCl concurrently with suppression HCl to PVC
Macromole decompose produce from caloytic action；Polyfunctionality fatty acid structure introduces in heat stabilizer molecule and may replace unstable chlorine atom
And eliminate thermal degradation initiation part and can improve PVC long-term thermal stability.
3. the Long carbon chain ester group in the liquid composite thermal stabilizer that the present invention prepares enhances and the compatibility of PVC molecule, overcomes
Little molecule heat stabilizer poor heat resistance, volatile and move out, thus reduce heat stabilizer loss in the PVC course of processing.
4. this liquid composite thermal stabilizer, is a kind of efficient liquid composite thermal stabilizer of asepsis environment-protecting, meets the need of energy-saving and emission-reduction
Ask.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of N-(3-amino-benzoic acid base) paulownia horse amic acid slaine；A. tong ma anhydride, b. is to amino
Benzoic acid, c.N-(3-amino-benzoic acid base) paulownia horse amic acid, d.N-(3-amino-benzoic acid base) paulownia horse amic acid calcium, e.N-(3-
Amino-benzoic acid base) paulownia horse amic acid zinc；
Fig. 2 is turning of the liquid calcium zinc composite PVC heat stabilizer prepared of the present invention and domestic commercially available Powdery calcium-zinc complex heat stabilizer
Square rheological curve figure.
Detailed description of the invention
Being not directed to part in literary composition the most same as the prior art maybe can use prior art to be realized.Following is the preferred of the present invention
Embodiment, but the present invention is also not limited to following only embodiment, is slightly modified the guarantor that also will be regarded as the present invention in embodiment
Protect scope.
Tong ma anhydride is commercially available prod, molecular weight 390.51, and structural formula is as follows:
Embodiment 1
(1) tong ma anhydride taking 78.10g (molecular weight 390.51,0.2mol) is dissolved in the ethyl acetate of 93.72g, adds
Enter in reaction vessel, be warmed up to 25～60 DEG C.By molten for 24.41g (molecular weight 137.14,0.178mol) para-amino benzoic acid
Solution, in the ethyl acetate of 317.33g, drops in reaction vessel, reacts 4h after dropping at such a temperature, and rotation is steamed, very
Sky is dried to obtain solid product N-(3-amino-benzoic acid base) paulownia horse amic acid.
(2) by 26.38g (molecular weight 527.65,0.05mol) N-(3-amino-benzoic acid base) paulownia horse amic acid and 26.38g
Diethylene glycol monobutyl ether joins in reaction vessel, is warming up to 70 DEG C.Until completely dissolved, 2 batches are divided to add 3.88g (molecular weight
81.39,0.0475mol) zinc oxide or 2.58g (molecular weight 56.08,0.046mol) calcium oxide, be warming up to 125 DEG C, dropping
The glacial acetic acid of 0.15g, be incubated 3h, sucking filtration, rotation be evaporated off water obtain liquid N-(3-amino-benzoic acid base) paulownia horse amic acid zinc salt or
N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt.
(3) by 8g liquid N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt and 2g N-(3-amino-benzoic acid base) paulownia horse acyl
Amino acid zinc salt compounds, and obtains liquid composite thermal stabilizer.
N-(3-amino-benzoic acid base) paulownia horse amic acid prepared by the present embodiment, N-(3-amino-benzoic acid base) paulownia horse amic acid calcium and
The infrared spectrogram of N-(3-amino-benzoic acid base) paulownia horse amic acid zinc is shown in (c), (d), (e) in Fig. 1 respectively.In Fig. 1 (a)
Tong ma anhydride is at 1865cm-1And 1786cm-1Near be antisymmetry and the symmetrical stretching vibration absworption peak of C=O in cyclic acid anhydride；
1600cm in (b) in Fig. 1-1Neighbouring is C=C skeletal vibration absworption peak, 3100-3000cm in phenyl ring-1For C-H in phenyl ring
Stretching vibration absworption peak, 843cm-1Neighbouring is that in phenyl ring, the disubstituted C-H of para-position bends absworption peak, 3461cm-1And 3364cm-1
For the absworption peak of NH in primary amine.In FIG in (c) N-(3-amino-benzoic acid base) paulownia horse amic acid at 1865cm-1With 1786
cm-1Vicinity, without absworption peak, shows that cyclic acid anhydride converts the most completely；3461cm-1And 3364cm-1Vicinity is without absworption peak, table
Bright primary amine converts the most completely；At 1603cm-1、843cm-1And 3000cm-1There is the characteristic absorption peak on phenyl ring in place, exists simultaneously
3333cm-1Place, 1635cm-1、1523cm-1Place and 1286cm-1Occur respectively the NH stretching vibration absworption peak in secondary amide,
C=O stretching vibration absworption peak, NH bending and C-N stretching vibration absworption peak, show tong ma anhydride and para-amino benzoic acid reaction
After generate N-(3-amino-benzoic acid base) paulownia horse amic acid.With (c) N-in Fig. 1 (3-amino-benzoic acid base) paulownia horse amic acid phase
Ratio, (e) N-(3-amino-benzoic acid base) paulownia horse in (d) N-(3-amino-benzoic acid base) paulownia horse amic acid calcium and Fig. 1 in Fig. 1
Amic acid zinc is respectively at 1692cm-1Vicinity is almost without absworption peak, simultaneously at 1413cm-1Near and 1530cm-1There is carboxylic in place
The symmetrical stretching vibration absworption peak of acid soap and antisymmetric stretching vibration absworption peak, show to there occurs that acid generates salt.
Embodiment 2
(1) tong ma anhydride taking 78.10g is dissolved in the ethyl acetate of 78.10g, joins in reaction vessel, is warmed up to
25～60 DEG C.22.90g para-amino benzoic acid is dissolved in the ethyl acetate of 343.50g, drops in reaction vessel, dropping
After react 4h at such a temperature, rotation is steamed, vacuum drying obtains solid product N-(3-amino-benzoic acid base) paulownia horse amic acid.
(2) by 26.38g N-(3-amino-benzoic acid base) paulownia horse amic acid, 7.91g diethylene glycol monobutyl ether and 7.91g tasteless kerosene
Join in reaction vessel, be warming up to 70 DEG C.Until completely dissolved, 3 batches are divided to add 3.70g zinc oxide or 2.80g oxidation
Calcium, is warming up to 120 DEG C, the hydrogen peroxide of dropping 0.05g, is incubated 3h, and sucking filtration, rotation are evaporated off water and obtain liquid N-(3-amino-benzene
Formyl) paulownia horse amic acid zinc salt or N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt.
(3) by 8g liquid N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt and 2g N-(3-amino-benzoic acid base) paulownia horse acyl
Amino acid zinc salt compounds, and obtains liquid composite thermal stabilizer.
Embodiment 3
(1) tong ma anhydride taking 78.10g is dissolved in the acetone of 117.15g, joins in reaction vessel, is warmed up to 25～60 DEG C.
22.90g para-amino benzoic acid is dissolved in the acetone of 458g, drops in reaction vessel, after dropping at such a temperature
Reaction 4h, rotation is steamed, vacuum drying obtains solid product N-(3-amino-benzoic acid base) paulownia horse amic acid.
(2) 26.38g N-(3-amino-benzoic acid base) paulownia horse amic acid and 7.91g diethylene glycol monobutyl ether are joined reaction vessel
In, it is warming up to 70 DEG C.Until completely dissolved, point 3 batches of addition 3.70g zinc oxide or 2.80g calcium oxide, it is warming up to 120 DEG C,
The glacial acetic acid of dropping 0.05g, is incubated 3h, and sucking filtration, rotation are evaporated off water and obtain liquid N-(3-amino-benzoic acid base) paulownia horse amic acid zinc
Salt or N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt.
(3) by 6g liquid N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt and 2g N-(3-amino-benzoic acid base) paulownia horse acyl
Amino acid zinc compounds, and obtains liquid composite thermal stabilizer.
Embodiment 4
(1) tong ma anhydride taking 78.10g is dissolved in the acetone of 93.72g, joins in reaction vessel, is warmed up to 25～60 DEG C.
22.90g para-amino benzoic acid is dissolved in the acetone of 412.20g, drops in reaction vessel, in this temperature after dropping
Lower reaction 4h, rotation is steamed, vacuum drying obtains solid product N-(3-amino-benzoic acid base) paulownia horse amic acid.
(2) by 26.38g N-(3-amino-benzoic acid base) paulownia horse amic acid, 13.19g diethylene glycol monobutyl ether and the tasteless coal of 13.19g
Oil joins in reaction vessel, is warming up to 70 DEG C.Until completely dissolved, 3 batches are divided to add 3.70g zinc oxide or 2.80g oxygen
Change calcium, be warming up to 120 DEG C, dropping 0.26g hydrogen peroxide, be incubated 3h, sucking filtration, rotation be evaporated off water obtain liquid N-(3-amino-
Benzoxy) paulownia horse amic acid zinc salt or N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt.
(3) by 6g liquid N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt and 2g N-(3-amino-benzoic acid base) paulownia horse acyl
Amino acid zinc compounds, and obtains liquid composite thermal stabilizer.
Embodiment 5
(1) tong ma anhydride taking 78.10g is dissolved in the acetone of 93.72g, joins in reaction vessel, is warmed up to 25～60 DEG C.
22.90g para-amino benzoic acid is dissolved in the acetone of 412.20g, drops in reaction vessel, in this temperature after dropping
Lower reaction 4h, rotation is steamed, vacuum drying obtains solid product N-(3-amino-benzoic acid base) paulownia horse amic acid.
(2) 26.38g N-(3-amino-benzoic acid base) paulownia horse amic acid and 13.19g diethylene glycol monobutyl ether are joined reaction vessel
In, it is warming up to 70 DEG C.Until completely dissolved, point 3 batches of addition 3.33g zinc oxide or 2.52g calcium oxide, it is warming up to 120 DEG C,
The glacial acetic acid of dropping 0.26g, is incubated 3h, and sucking filtration, rotation are evaporated off water and obtain liquid N-(3-amino-benzoic acid base) paulownia horse amic acid zinc
Salt or N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt.
(3) by 6g liquid N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt and 2g N-(3-amino-benzoic acid base) paulownia horse acyl
Amino acid zinc compounds, and obtains liquid composite thermal stabilizer.
Embodiment 6
(1) tong ma anhydride taking 78.10g is dissolved in the acetone of 93.72g, joins in reaction vessel, is warmed up to 25～60 DEG C.
22.90g para-amino benzoic acid is dissolved in the acetone of 412.20g, drops in reaction vessel, in this temperature after dropping
Lower reaction 4h, rotation is steamed, vacuum drying obtains solid product N-(3-amino-benzoic acid base) paulownia horse amic acid.
(2) 26.38g N-(3-amino-benzoic acid base) paulownia horse amic acid and 26.38g diethylene glycol monobutyl ether are joined reaction vessel
In, it is warming up to 70 DEG C.Until completely dissolved, point 3 batches of addition 3.16g zinc oxide or 2.39g calcium oxide, it is warming up to 120 DEG C,
The glacial acetic acid of dropping 0.26g, is incubated 3h, and sucking filtration, rotation are evaporated off water and obtain liquid N-(3-amino-benzoic acid base) paulownia horse amic acid zinc
Salt or N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt.
(3) by 6g liquid N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt and 2g N-(3-amino-benzoic acid base) paulownia horse acyl
Amino acid zinc compounds, and obtains liquid composite thermal stabilizer.
Embodiment 7
(1) tong ma anhydride taking 78.10g is dissolved in the acetone of 117.15g, joins in reaction vessel, is warmed up to 25～60 DEG C.
22.90g para-amino benzoic acid is dissolved in the acetone of 458g, drops in reaction vessel, after dropping at such a temperature
Reaction 4h, rotation is steamed, vacuum drying obtains solid product N-(3-amino-benzoic acid base) paulownia horse amic acid.
(2) 26.38g N-(3-amino-benzoic acid base) paulownia horse amic acid and 21.10g diethylene glycol monobutyl ether are joined reaction vessel
In, it is warming up to 70 DEG C.Until completely dissolved, point 3 batches of addition 3.70g zinc oxide or 2.80g calcium oxide, it is warming up to 120 DEG C,
The hydrogen peroxide of dropping 0.13g, is incubated 3h, and sucking filtration, rotation are evaporated off water and obtain liquid N-(3-amino-benzoic acid base) paulownia horse amic acid zinc
Salt or N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt.
(3) by 6g liquid N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt and 2g N-(3-amino-benzoic acid base) paulownia horse acyl
Amino acid zinc compounds, and obtains liquid composite thermal stabilizer.
Embodiment 8
(1) tong ma anhydride taking 78.10g is dissolved in the acetone of 93.72g, joins in reaction vessel, is warmed up to 25～60 DEG C.
22.90g para-amino benzoic acid is dissolved in the acetone of 412.20g, drops in reaction vessel, in this temperature after dropping
Lower reaction 4h, rotation is steamed, vacuum drying obtains solid product N-(3-amino-benzoic acid base) paulownia horse amic acid.
(2) 26.38g N-(3-amino-benzoic acid base) paulownia horse amic acid and 26.38g diethylene glycol monobutyl ether are joined reaction vessel
In, it is warming up to 70 DEG C.Until completely dissolved, point 3 batches of addition 3.70g zinc oxide or 2.80g calcium oxide, it is warming up to 120 DEG C,
The glacial acetic acid of dropping 0.13g, is incubated 3h, and sucking filtration, rotation are evaporated off water and obtain liquid N-(3-amino-benzoic acid base) paulownia horse amic acid zinc
Salt or N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt.
(3) by 6g liquid N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt and 2g N-(3-amino-benzoic acid base) paulownia horse acyl
Amino acid zinc compounds, and obtains liquid composite thermal stabilizer.
Comparative example 1:
By brand calcium zinc heat stabilizer conventional in the market and homemade calcium zinc heat stabilizer in the feelings of the same consumption of same formula
Under condition, compare the performance of its PVC product.
Experimental group 1:
Table 1 experimental group 1 forms
| Raw material | Consumption (g) |
| PVC | 100 |
| DOTP | 40 |
| The liquid calcium Zn composite heat stabilizer of embodiment 1 preparation | 3 |
Contrast groups 1:
Table 2 contrast groups 1 forms
| Raw material | Consumption (g) |
| PVC | 100 |
| DOTP | 40 |
| Calcium stearate | 2.25 |
| Zinc stearate | 0.75 |
Contrast groups 2:
Table 3 contrast groups 2 forms
| Raw material | Consumption (g) |
| PVC | 100 |
| DOTP | 30 |
| Calcium stearate | 2.25 |
| Zinc stearate | 0.75 |
Contrast groups 3:
Table 4 contrast groups 3 forms
| Raw material | Consumption (g) |
| PVC | 100 |
| DOTP | 30 |
| Domestic commercially available Ca-Zn composite heat stabilizer | 3 |
Contrast groups 4:
Table 5 contrast groups 4 forms
| Raw material | Consumption (g) |
| PVC | 100 |
| DOTP | 40 |
| Domestic commercially available Ca-Zn composite heat stabilizer | 3 |
Tensile property is tested: use AHTM D638Type V dumbbell shape mould, note in HAAKE (German) MiniJet II
It is moulded dumb-bell shape tensile bars drawing zone thickness 3.18mm, width 3.18mm, original gauge length 7.62mm.Use CMT400
Type microcomputer controlled electronic universal tester (Shenzhen is newly thought carefully), by ASTM D638-2003 " plastic tensile method for testing performance "
Measuring the tensile property of material, extension test speed is 10mm/min, often group six samples of parallel testing.
Static heat stability is tested: respectively by experimental group 1, the material mix homogeneously of contrast groups 1 to contrast groups 4 formula, take
60.0g on torque rheometer 165-170 DEG C, plasticate under rotating speed 40r/min 3min, then utilizes the miniature plate vulcanizer will
Sizing material is all pressed into the test piece of 1mm thickness.GB/T2917.1-2002 Congo Red test method is utilized to investigate product at 185 DEG C quiet
The quality of state heat stability.
Dynamic thermal stability is tested: respectively by experimental group 1, the material mix homogeneously of contrast groups 1 to contrast groups 4 formula, take 64g
Sample is tested on torque rheometer, initial value rotating speed: 30.0r/min；Milling device test point: T1=180.5 DEG C, T2=180.9 DEG C,
T3=182.3 DEG C.
On the premise of not affecting plasticizing capacity, investigate the self-control liquid calcium Zn composite heat stabilizer impact on PVC heat stability.
Experimental group, contrast groups 1 and the static heat stability of contrast groups 4, dynamic thermal stability and mechanical property experimental results are shown in Table respectively
6, table 7 and Fig. 2.Understand based on the above results: be combined with domestic commercially available Ca-Zn composite heat stabilizer and calcium stearate/zinc stearate
Thermally-stabilised comparing, self-control liquid calcium Zn composite heat stabilizer has more excellent long-term thermal stability, and to mechanical property without bad
Impact.
Table 6 experimental group contrasts with the static heat stability of contrast groups heat stabilizer
Table 7 experimental group and the contrast to PVC product mechanical property of the contrast groups heat stabilizer
Note: above several groups all according to following standard sample preparation and test.The tensile property of PVC product is with reference to GB/T 1040.1-2006
" plastic tensile test method ", uses CMT4000 type microcomputer controlled electronic universal tester (Shenzhen is newly thought carefully), measures material
The tensile property of material and bending property, extension test speed is 50mm/min, and Mechanics Performance Testing temperature is 25 DEG C.
Claims (9)
1. the preparation method of a heat stabilizer for PVC, it is characterised in that prepared by following steps:
The first step: take after tong ma anhydride is dissolved in solvent orange 2 A and join in reaction vessel, it is warming up to 25 ~ 60 DEG C, by para-amino benzoic acid by being dissolved in solvent orange 2 A with tong ma anhydride 1:1 ~ 1.2 in molar ratio, and drop in reaction vessel, isothermal reaction 1 ~ 4 h after dropping, vacuum drying, obtains solid product N-(3-amino-benzoic acid base) paulownia horse amic acid；Solvent orange 2 A used is at least one in ethyl acetate, acetone, ethanol and glacial acetic acid, and twice consumption is respectively tong ma anhydride and 1-20 times of para-amino benzoic acid quality；
Second step: by N-(3-amino-benzoic acid base) paulownia horse amic acid and solvent B 1:1 in mass ratio
~ 0.3 joins in reaction vessel, is warming up to 50 ~ 90 DEG C；Until completely dissolved, by being to be dividedly in some parts metal-oxide or metal hydroxides at 0.9 ~ 1: 1 with N-(3-amino-benzoic acid base) paulownia horse amic acid mol ratio, it is warming up to 100 ~ 140 DEG C, dropping accounts for the catalyst C of N-(3-amino-benzoic acid base) paulownia horse amic acid mass fraction 0.2 ~ 1 %, insulation 2 ~ 5 h, rotation is evaporated off water, and sucking filtration obtains liquid N-(3-amino-benzoic acid base) paulownia horse amic acid slaine；Described solvent B is at least one in petroleum ether, tasteless kerosene, propylene glycol monomethyl ether, diethylene glycol monobutyl ether；Described metal-oxide is calcium oxide or zinc oxide, described metal hydroxides is calcium hydroxide, finally gives liquid N-(3-amino-benzoic acid base) paulownia horse amic acid metal calcium salt and liquid N-(3-amino-benzoic acid base) paulownia horse amic acid metal zinc salt；Catalyst C is at least one in hydrogen peroxide, glacial acetic acid；
3rd step: prepared liquid N-(3-amino-benzoic acid base) paulownia horse amic acid calcium salt is compounded with N-(3-amino-benzoic acid base) paulownia horse amic acid zinc salt 4 ~ 3:1 in mass ratio, obtains liquid composite thermal stabilizer.
The preparation method of a kind of heat stabilizer for PVC, it is characterised in that described solvent orange 2 A is ethyl acetate, consumption is respectively 1 times of tong ma anhydride quality, 10 times of para-amino benzoic acid quality.
The preparation method of a kind of heat stabilizer for PVC, it is characterised in that described para-amino benzoic acid is 1:1 ~ 1.2 by the mol ratio with tong ma anhydride, the response time is 4 h.
The preparation method of a kind of heat stabilizer for PVC, it is characterised in that described solvent B is diethylene glycol monobutyl ether, consumption is equal with N-(3-amino-benzoic acid base) paulownia horse amic acid quality.
The preparation method of a kind of heat stabilizer for PVC, it is characterised in that described metal-oxide is calcium oxide and zinc oxide, consumption be respectively with mol ratio 1:1 of N-(3-amino-benzoic acid base) paulownia horse amic acid.
The preparation method of a kind of heat stabilizer for PVC, it is characterised in that described catalyst C is glacial acetic acid, accounts for N-(3-amino-benzoic acid base) paulownia horse amic acid mass fraction 0.57%.
The preparation method of a kind of heat stabilizer for PVC, it is characterised in that described N-(3-amino-benzoic acid base) paulownia horse amic acid calcium is 4:1 with the mass ratio of N-(3-amino-benzoic acid base) paulownia horse amic acid zinc.
8. the heat stabilizer for PVC that the arbitrary described method of claim 1 ~ 7 is prepared.
9. the heat stabilizer that the arbitrary described method of claim 1 ~ 7 is prepared application in preparation PVC product.
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| CN110194873A (en) * | 2019-05-17 | 2019-09-03 | 许艳辉 | A kind of modified additive preparation process improving PVC material thermal stability |
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