CN106800670B - Tung oil base binary amic acid calcium-zinc composite liquid heat stabilizer and its preparation method and application - Google Patents
Tung oil base binary amic acid calcium-zinc composite liquid heat stabilizer and its preparation method and application Download PDFInfo
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- CN106800670B CN106800670B CN201611203603.7A CN201611203603A CN106800670B CN 106800670 B CN106800670 B CN 106800670B CN 201611203603 A CN201611203603 A CN 201611203603A CN 106800670 B CN106800670 B CN 106800670B
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- aminophenyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
Tong ma anhydride and diamine are obtained tung oil base binary amic acid through the aminolysis reaction of acid anhydrides by tung oil base binary amic acid calcium-zinc composite liquid heat stabilizer and its preparation method and application；Tung oil base binary amic acid and metal oxide or metal hydroxides are prepared into liquid tung oil base binary amide acid metal salt through single step reaction under solvent；Liquid tung oil base binary amide acid calcium salt obtained is compounded with zinc salt, obtains liquid composite thermal stabilizer.Liquid Ca-Zn composite heat stabilizer prepared by the present invention has the characteristics that nontoxic, heavy metal free, environmental protection, it is a kind of efficient composite fluid heat stabilizer, with PVC compatibility it is good, be easy dispersion, while assign the more preferable thermal stability of PVC product, the transparency, plasticising performance.The preparation process route is simple and environmentally-friendly, and raw material sources are abundant and cheap.
Description
Technical field
The invention belongs to plastic additive fields, and in particular to a kind of tung oil base binary amic acid calcium-zinc composite liquid heat is steady
Determine agent and its preparation method and application.
Background technique
There are many defect sturctures in polyvinyl chloride (PVC) molecular structure, such as branch, tertiary chlorine atom, allyl chloride, end
With chain internal double bond, oxygen-containing group etc., these structures are the basic reasons for causing it unstable at processing temperatures, degradable.With
Deepening constantly for palliating degradation degree, the color of polyvinyl chloride resin constantly deepen, until close to black, and the mechanical property of product
Seriously destroyed.Therefore, heat stabilizer occupies especially important status in plastics processing.
Common heat stabilizer currently on the market, such as lead heat stabilizer, organo-tin het stabilizer, product thermal stability
Excellent but its use is increasingly restricted.And common calcium stearate/zinc heat stabilizer generally requires and other auxiliary heat
The thermal stability that can just significantly improve PVC is used in combination in stabilizer such as polyalcohol, beta-diketon, phosphite ester, this is often improved
Economic cost.Therefore it studies and develops novel and multifunctional calcium zinc heat stabilizer and replace or partially replace environmentally harmful or high price
Heat stabilizer (such as lead salt, barium, cadmium and organotin) have great importance.
A kind of tung oil base binary amic acid calcium-zinc composite liquid heat stabilizer is developed by raw material of tong ma anhydride in this research,
The heat stabilizer has the characteristics that nontoxic, heavy metal free, environmental protection, and the thermal stability that can significantly improve PVC product assigns again simultaneously
Its better transparency and plasticizing capacity.The present invention has from the aspects of resource selection, material property and natural environmental-protective three
It is significant.
Summary of the invention
The technical issues of solution: the present invention is that existing calcium zinc heat stabilizer product is single in the market for reply, provides one
Kind tung oil base binary amic acid calcium-zinc composite liquid heat stabilizer and its preparation method and application.
Technical solution: tung oil base binary amic acid calcium-zinc composite liquid heat stabilizer, general structure are as follows:
Wherein M is Ca or Zn, and tung oil base binary amide acid calcium salt and tung oil base binary amic acid zinc salt 5~3:1 in mass ratio
Compounding.
The preparation method of tung oil base binary amic acid calcium-zinc composite liquid heat stabilizer, is made by following steps:
Step 1: being added in reaction vessel after taking tong ma anhydride to be dissolved in solvent A, 35~60 DEG C are warming up to, by binary
Amine is added dropwise in reaction vessel by 1:2.1~2.2 are dissolved in solvent A in molar ratio with tong ma anhydride, and rear constant temperature is added dropwise
1~6h is reacted, revolving removes solvent, obtains product liquid tung oil base binary amic acid；Solvent A used be ethyl acetate, acetone,
At least one of ethyl alcohol and tetrahydrofuran, dosage is respectively 1-25 times of tong ma anhydride and diamine quality twice；
Step 2: tung oil base binary amic acid and 1:(1~2 in mass ratio solvent B) it is added in reaction vessel, it is warming up to
70℃；After stirring 30min, be (0.9~1) by with tung oil base binary amic acid molar ratio: 1 is added portionwise metal oxide or gold
Belong to hydroxide, be warming up to 110 DEG C, the catalyst C for accounting for tung oil base binary amide acid mass fraction 0.2~1%, heat preservation is added dropwise
0.5~4h, revolving water removal, suction filtration obtain liquid tung oil base binary amide acid metal salt；The solvent B is petroleum ether, tasteless coal
Oil, atoleine, 200# solvent naphtha, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol ether, in diethylene glycol dimethyl ether
At least one；The metal oxide is calcium oxide or zinc oxide, and the metal hydroxides is calcium hydroxide, is finally obtained
Liquid tung oil base binary amic acid metal calcium salt or liquid tung oil base binary amic acid metal zinc salt；Catalyst C is hydrogen peroxide, ice
At least one of acetic acid；
Step 4: in mass ratio by liquid tung oil base binary amide acid calcium salt obtained and tung oil base binary amic acid zinc salt
5~3:1 compounding, obtains liquid composite thermal stabilizer.
Preferably, the solvent A is tetrahydrofuran, and dosage is respectively 1 times of tong ma anhydride quality, the 1- of diamine quality
25 times.
Preferably, the diamine be ethylenediamine, hexamethylene diamine, propane diamine, p-phenylenediamine, 4-4'-diaminodiphenyl ether,
Bis- (3- amino-benzene oxygen) benzene of 1-3-, bis- (4- amino-benzene oxygen) benzene of 1-3-, bis- [4- (4- amino-benzene oxygen) benzene of 2-2'-
Base] any one in propane.
Preferably, the solvent B is diethylene glycol monobutyl ether, and dosage is equal with tung oil base binary amic acid quality.
Preferably, the metal oxide or metal hydroxides dosage are mole with tung oil base binary amic acid respectively
Than 0.94:1,4h is reacted.
Preferably, the catalyst C is glacial acetic acid, accounts for tung oil base binary amide acid mass fraction 0.65%.
Preferably, the mass ratio of the tung oil base binary amic acid calcium and tung oil base binary amic acid zinc is 4:1.
Application of the tung oil base binary amic acid calcium-zinc composite liquid heat stabilizer in preparation PVC product
The utility model has the advantages that raw material sources are abundant 1. using tung oil as raw material in the present invention, get rid of to petrochemical industry resource according to
Rely.
2. with using common fats acid as the heat stabilizer of basic framework compared with, tung oil base binary amic acid produced by the present invention
Introduced in metal salt and have both multiple functional groups of a variety of following functions: binary amide structure can more effectively capture chlorine radical and
Absorb HCl；Polyfunctionality fatty acid structure, which may replace unstable chlorine atom (i.e. elimination thermal degradation causes part), can be improved PVC long
Phase thermal stability；The conjugated polyene structure addition that polynary double bond is generated with thermal degradation in PVC, prevents it from further increasing and shorten
Conjugated polyene segment can significantly mitigate its coloring.
It is a kind of 3. Ca-Zn liquid composite thermal stabilizer prepared by the present invention has the characteristics that nontoxic, heavy metal free, environmental protection
Efficient composite fluid heat stabilizer, meets the demand of energy-saving and emission-reduction.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of tung oil base binary amide acid metal salt；A. tong ma anhydride, b. p-phenylenediamine, c.N- (3-
Aminophenyl) paulownia horse amic acid, d.N- (3- aminophenyl) paulownia horse amic acid calcium, e.N- (3- aminophenyl) paulownia horse amic acid zinc.
Specific embodiment
Part is not directed in text to be the same as those in the prior art or can be realized by using the prior art.Following is the present invention
Preferred embodiment, but the present invention is also not limited to following only embodiment, is slightly modified also in embodiment and will be regarded as this
The protection scope of invention.
Embodiment 1
(1) tong ma anhydride of 82.01g (molecular weight 390.51,0.21mol) is taken to be dissolved in the tetrahydrofuran of 82.01g,
It is added in reaction vessel, is warming up to 45 DEG C.10.81g (molecular weight 108.14,0.1mol) p-phenylenediamine is dissolved in 200g's
It in tetrahydrofuran, is added dropwise in reaction vessel, in 45 DEG C of reaction 5h after being added dropwise, revolving, vacuum drying obtain product liquid
N- (2- aminophenyl) paulownia horse amic acid (APTMA).
(2) by 0.05mol N- (2- aminophenyl) paulownia horse amic acid and etc. quality diethylene glycol monobutyl ether be added to reaction hold
In device, it is warming up to 75 DEG C.Until completely dissolved, in two batches or more batches addition 0.047mol zinc oxide or calcium hydroxide, heating
To 110 DEG C, the glacial acetic acid or hydrogen peroxide for accounting for N- (2- aminophenyl) paulownia horse amide acid mass fraction 0.65% is added dropwise, keeps the temperature 4h, takes out
Filter, revolving water removal obtain liquid N- (2- aminophenyl) paulownia horse amic acid zinc salt (APTMA-Zn) or N- (2- aminophenyl) paulownia horse amide
Acid calcium salt (APTMA-Ca).
(3) 8g N- (2- aminophenyl) paulownia horse amide acid calcium salt and 2g N- (2- aminophenyl) paulownia horse amic acid zinc salt is multiple
Match, obtains liquid composite thermal stabilizer.
N- (2- aminophenyl) paulownia horse amic acid, N- (2- aminophenyl) paulownia horse amic acid calcium and N- (2- manufactured in the present embodiment
Aminophenyl) infrared spectrogram of paulownia horse amic acid zinc is shown in (c), (d), (e) in Fig. 1 respectively.
N- (2- aminophenyl) paulownia horse amic acid is in 1865cm in Fig. 1 (c)-1And 1786cm-1Vicinity absorption peak obviously subtracts
It is weak, show that cyclic acid anhydride almost converts；In 1440cm-1、1162cm-1And 838cm-1There is the characteristic absorption on phenyl ring in place
Peak, while in 1610cm-1、1558cm-1Place and 1310cm-1Occurs the NH stretching vibration absworption peak in secondary amide respectively, C=O stretches
Contracting vibration absorption peak, NH bending and C-N stretching vibration absworption peak generate N- after showing tong ma anhydride and p-phenylenediamine reaction
(2- aminophenyl) paulownia horse amic acid.It is compared with Fig. 1 (c) N- (2- aminophenyl) paulownia horse amic acid, Fig. 1 (d) N- (2- aminophenyl) paulownia
Horse amic acid calcium and (e) N- (2- aminophenyl) paulownia horse amic acid zinc are respectively in 1692cm-1Vicinity almost without absorption peak, while
1456cm-1Neighbouring and 1515cm-1There is the symmetrical stretching vibration absorption peak of carboxylic soap and antisymmetric stretching vibration absorption peak in place,
Show that acid, which has occurred, generates salt.Following embodiment, which prepares tung oil base binary amide acid metal salt, to be had and the basic phase of embodiment 1
Same infrared spectroscopy, no longer specifically describes.
Embodiment 2
(1) tong ma anhydride of 82.01g (molecular weight 390.51,0.21mol) is taken to be dissolved in the tetrahydrofuran of 82.01g,
It is added in reaction vessel, is warming up to 45 DEG C.10.81g (molecular weight 108.14,0.1mol) p-phenylenediamine is dissolved in
It in the tetrahydrofuran of 270.25g, is added dropwise in reaction vessel, reacts 5h at 45 DEG C after being added dropwise, rotate, be dried in vacuo
To product liquid N- (2- aminophenyl) paulownia horse amic acid.
(2) by 0.05mol N- (2- aminophenyl) paulownia horse amic acid and etc. quality diethylene glycol monobutyl ether be added to reaction hold
In device, it is warming up to 75 DEG C.Until completely dissolved, in two batches or more batches addition 0.047mol zinc oxide or calcium hydroxide, heating
To 110 DEG C, the glacial acetic acid or hydrogen peroxide for accounting for N- (2- aminophenyl) paulownia horse amide acid mass fraction 0.65% is added dropwise, keeps the temperature 4h, takes out
Filter, revolving water removal obtain liquid N- (2- aminophenyl) paulownia horse amic acid zinc salt or N- (2- aminophenyl) paulownia horse amide acid calcium salt.
(3) 8g N- (2- aminophenyl) paulownia horse amide acid calcium salt and 2g N- (2- aminophenyl) paulownia horse amic acid zinc salt is multiple
Match, obtains liquid composite thermal stabilizer.
Embodiment 3
(1) tong ma anhydride of 80.05g (molecular weight 390.51,0.205mol) is taken to be dissolved in the tetrahydrofuran of 80.05g,
It is added in reaction vessel, is warming up to 45 DEG C.10.81g (molecular weight 108.14,0.1mol) p-phenylenediamine is dissolved in
It in the tetrahydrofuran of 270.25g, is added dropwise in reaction vessel, is reacting 5h, revolving, vacuum drying at 45 DEG C after being added dropwise
Obtain product liquid N- (2- aminophenyl) paulownia horse amic acid.
(2) by 0.05mol N- (2- aminophenyl) paulownia horse amic acid and etc. quality diethylene glycol monobutyl ether be added to reaction hold
In device, it is warming up to 75 DEG C.Until completely dissolved, in two batches or more batches addition 0.047mol zinc oxide or calcium hydroxide, heating
To 110 DEG C, the glacial acetic acid or hydrogen peroxide for accounting for N- (2- aminophenyl) paulownia horse amide acid mass fraction 0.65% is added dropwise, keeps the temperature 4h, takes out
Filter, revolving water removal obtain liquid N- (2- aminophenyl) paulownia horse amic acid zinc salt or N- (2- aminophenyl) paulownia horse amide acid calcium salt.
(3) 8g N- (2- aminophenyl) paulownia horse amide acid calcium salt and 2g N- (2- aminophenyl) paulownia horse amic acid zinc salt is multiple
Match, obtains liquid composite thermal stabilizer.
Embodiment 4
(1) tong ma anhydride of 80.05g (molecular weight 390.51,0.205mol) is taken to be dissolved in the tetrahydrofuran of 80.05g,
It is added in reaction vessel, is warming up to 45 DEG C.10.81g (molecular weight 108.14,0.1mol) p-phenylenediamine is dissolved in
It in the tetrahydrofuran of 237.82g, is added dropwise in reaction vessel, is reacting 5h, revolving, vacuum drying at 45 DEG C after being added dropwise
Obtain product liquid N- (2- aminophenyl) paulownia horse amic acid.
(2) by 0.05mol N- (2- aminophenyl) paulownia horse amic acid and etc. quality diethylene glycol monobutyl ether be added to reaction hold
In device, it is warming up to 75 DEG C.Until completely dissolved, in two batches or more batches addition 0.047mol zinc oxide or calcium hydroxide, heating
To 110 DEG C, the glacial acetic acid or hydrogen peroxide for accounting for N- (2- aminophenyl) paulownia horse amide acid mass fraction 0.65% is added dropwise, keeps the temperature 4h, takes out
Filter, revolving water removal obtain liquid N- (2- aminophenyl) paulownia horse amic acid zinc salt or N- (2- aminophenyl) paulownia horse amide acid calcium salt.
(3) 8g N- (2- aminophenyl) paulownia horse amide acid calcium salt and 2g N- (2- aminophenyl) paulownia horse amic acid zinc salt is multiple
Match, obtains liquid composite thermal stabilizer.
Embodiment 5
(1) tong ma anhydride of 85.91g (molecular weight 390.51,0.22mol) is taken to be dissolved in the tetrahydrofuran of 85.91g,
It is added in reaction vessel, is warming up to 45 DEG C.10.81g (molecular weight 108.14,0.1mol) p-phenylenediamine is dissolved in
It in the tetrahydrofuran of 237.82g, is added dropwise in reaction vessel, is reacting 5h, revolving, vacuum drying at 45 DEG C after being added dropwise
Obtain product liquid N- (2- aminophenyl) paulownia horse amic acid.
(2) by 0.05mol N- (2- aminophenyl) paulownia horse amic acid and etc. quality diethylene glycol monobutyl ether be added to reaction hold
In device, it is warming up to 75 DEG C.Until completely dissolved, in two batches or more batches addition 0.047mol zinc oxide or calcium hydroxide, heating
To 110 DEG C, the glacial acetic acid or hydrogen peroxide for accounting for N- (2- aminophenyl) paulownia horse amide acid mass fraction 0.65% is added dropwise, keeps the temperature 4h, takes out
Filter, revolving water removal obtain liquid N- (2- aminophenyl) paulownia horse amic acid zinc salt or N- (2- aminophenyl) paulownia horse amide acid calcium salt.
(3) 8g N- (2- aminophenyl) paulownia horse amide acid calcium salt and 2g N- (2- aminophenyl) paulownia horse amic acid zinc salt is multiple
Match, obtains liquid composite thermal stabilizer.
Embodiment 6
(1) tong ma anhydride of 82.01g (molecular weight 390.51,0.21mol) is taken to be dissolved in the tetrahydrofuran of 82.01g,
It is added in reaction vessel, is warming up to 50 DEG C.10.81g (molecular weight 108.14,0.1mol) p-phenylenediamine is dissolved in 200mL
Tetrahydrofuran in, be added dropwise in reaction vessel, reacting 4h at 45 DEG C after being added dropwise, revolving, vacuum drying obtain liquid
Body product N- (2- aminophenyl) paulownia horse amic acid.
(2) by 0.05mol N- (2- aminophenyl) paulownia horse amic acid and etc. quality diethylene glycol monobutyl ether be added to reaction hold
In device, it is warming up to 75 DEG C.Until completely dissolved, in two batches or more batches addition 0.047mol zinc oxide or calcium hydroxide, heating
To 110 DEG C, the glacial acetic acid or hydrogen peroxide for accounting for N- (2- aminophenyl) paulownia horse amide acid mass fraction 0.65% is added dropwise, keeps the temperature 4h, takes out
Filter, revolving water removal obtain liquid N- (2- aminophenyl) paulownia horse amic acid zinc salt or N- (2- aminophenyl) paulownia horse amide acid calcium salt.
(3) 8g N- (2- aminophenyl) paulownia horse amide acid calcium salt and 2g N- (2- aminophenyl) paulownia horse amic acid zinc salt is multiple
Match, obtains liquid composite thermal stabilizer.
Embodiment 7
(1) tong ma anhydride of 85.91g (molecular weight 390.51,0.21mol) is taken to be dissolved in the tetrahydrofuran of 82.01g,
It is added in reaction vessel, is warming up to 45 DEG C.10.81g (molecular weight 108.14,0.1mol) ethylenediamine is dissolved in 18.03g's
It in tetrahydrofuran, is added dropwise in reaction vessel, is reacting 5h at 45 DEG C after being added dropwise, revolving, vacuum drying obtain liquid
Product N- (2- aminoethyl) paulownia horse amic acid (AETMA).
(2) by 0.05mol N- (2- aminoethyl) paulownia horse amic acid and etc. quality diethylene glycol monobutyl ether be added to reaction hold
In device, it is warming up to 75 DEG C.Until completely dissolved, in two batches or more batches addition 0.047mol zinc oxide or calcium hydroxide, heating
To 110 DEG C, the glacial acetic acid or hydrogen peroxide for accounting for N- (2- aminoethyl) paulownia horse amide acid mass fraction 0.65% is added dropwise, keeps the temperature 4h, takes out
Filter, revolving water removal obtain liquid N- (2- aminoethyl) paulownia horse amic acid zinc salt (AETMA-Zn) or N- (2- aminoethyl) paulownia horse amide
Acid calcium salt (AETMA-Ca).
(3.2) 8g N- (2- aminoethyl) paulownia horse amide acid calcium salt and 2g N- (2- aminoethyl) paulownia horse amic acid zinc salt is multiple
Match, obtains liquid composite thermal stabilizer.
Embodiment 8
(1) tong ma anhydride of 82.01g (molecular weight 390.51,0.21mol) is taken to be dissolved in the tetrahydrofuran of 82.01g,
It is added in reaction vessel, is warming up to 40 DEG C.10.81g (molecular weight 108.14,0.1mol) ethylenediamine is dissolved in 18.03g's
It in tetrahydrofuran, is added dropwise in reaction vessel, is reacting 4h at 45 DEG C after being added dropwise, revolving, vacuum drying obtain liquid
Product N- (2- aminoethyl) paulownia horse amic acid.
(2) by 0.05mol N- (2- aminoethyl) paulownia horse amic acid and etc. quality diethylene glycol monobutyl ether be added to reaction hold
In device, it is warming up to 75 DEG C.Until completely dissolved, in two batches or more batches addition 0.047mol zinc oxide or calcium hydroxide, heating
To 110 DEG C, the glacial acetic acid or hydrogen peroxide for accounting for N- (2- aminoethyl) paulownia horse amide acid mass fraction 0.65% is added dropwise, keeps the temperature 4h, takes out
Filter, revolving water removal obtain liquid N- (2- aminoethyl) paulownia horse amic acid zinc salt or N- (2- aminoethyl) paulownia horse amide acid calcium salt.
(3) 8g N- (2- aminoethyl) paulownia horse amide acid calcium salt is compounded with 2g N- (2- aminoethyl) paulownia horse amic acid zinc salt,
Obtain liquid composite thermal stabilizer.
Embodiment 9
(1) tong ma anhydride of 85.91g (molecular weight 390.51,0.22mol) is taken to be dissolved in the tetrahydrofuran of 85.91g,
It is added in reaction vessel, is warming up to 40 DEG C.10.81g (molecular weight 108.14,0.1mol) ethylenediamine is dissolved in 18.03g's
It in tetrahydrofuran, is added dropwise in reaction vessel, is reacting 4h at 45 DEG C after being added dropwise, revolving, vacuum drying obtain liquid
Product N- (2- aminoethyl) paulownia horse amic acid.
(2) by 0.05mol N- (2- aminoethyl) paulownia horse amic acid and etc. quality diethylene glycol monobutyl ether be added to reaction hold
In device, it is warming up to 75 DEG C.Until completely dissolved, in two batches or more batches addition 0.047mol zinc oxide or calcium hydroxide, heating
To 110 DEG C, the glacial acetic acid or hydrogen peroxide for accounting for N- (2- aminoethyl) paulownia horse amide acid mass fraction 0.65% is added dropwise, keeps the temperature 4h, takes out
Filter, revolving water removal obtain liquid N- (2- aminoethyl) paulownia horse amic acid zinc salt or N- (2- aminoethyl) paulownia horse amide acid calcium salt.
(3) 8g N- (2- aminoethyl) paulownia horse amide acid calcium salt and 2g N- (2- aminoethyl) paulownia horse amic acid zinc salt is multiple
Match, obtains liquid composite thermal stabilizer.
Comparative example 1:
Common calcium zinc heat stabilizer currently on the market and homemade calcium zinc heat stabilizer are incited somebody to action in the same same dosage of formula
In the case where (solid calcium zinc amount), compare the thermal stability of its PVC product.
Experimental group 1:
1 experimental group 1 of table composition
| Raw material | Dosage (g) |
| PVC | 100 |
| DOTP | 50 |
| Liquid Ca-Zn composite heat stabilizer prepared by embodiment 1 | 6 |
Experimental group 2:
2 experimental group 2 of table composition
| Raw material | Dosage (g) |
| PVC | 100 |
| DOTP | 50 |
| Liquid Ca-Zn composite heat stabilizer prepared by embodiment 7 | 6 |
Contrast groups 1:
2 contrast groups 1 of table composition
| Raw material | Dosage (g) |
| PVC | 100 |
| DOTP | 50 |
| Calcium stearate | 2.4 |
| Zinc stearate | 0.6 |
Contrast groups 2:
3 contrast groups 2 of table composition
| Raw material | Dosage (g) |
| PVC | 100 |
| DOTP | 40 |
| Calcium stearate | 2.4 |
| Zinc stearate | 0.6 |
Contrast groups 3:
4 contrast groups 3 of table composition
| Raw material | Dosage (g) |
| PVC | 100 |
| DOTP | 40 |
| Domestic commercially available Ca-Zn composite heat stabilizer | 3 |
Contrast groups 4:
5 contrast groups 4 of table composition
| Raw material | Dosage (g) |
| PVC | 100 |
| DOTP | 50 |
| Domestic commercially available Ca-Zn composite heat stabilizer | 3 |
Static heat stability experiment: the material for being respectively formulated experimental group 1, experimental group 2, contrast groups 1 and contrast groups 4 mixes
Uniformly, take 60.0g 160-165 DEG C on torque rheometer, plasticate 3min under revolving speed 40r/min, be pressed into the test piece of 1mm thickness.
The thermal stability of product is investigated according to ISO 182-1-1990 Congo Red test method and ISO 305-1990 (E).
Under the premise of not influencing plasticizing capacity, self-control liquid Ca-Zn composite heat stabilizer has been investigated to PVC thermal stability
Influence.Experimental group 1, experimental group 2, the thermal stability experimental result of contrast groups 1 and contrast groups 4 are as shown in table 6.In summary it ties
Known to fruit: with domestic commercially available Ca-Zn composite heat stabilizer and calcium stearate/zinc stearate compound thermal stable phase ratio, making liquid calcium by oneself
Zn composite heat stabilizer has superior long-term thermal stability, and has no adverse effects to mechanical property.
The static heat stability of 6 experimental group of table and contrast groups heat stabilizer compares
Claims (1)
1. the preparation method of tung oil base binary amic acid calcium-zinc composite liquid heat stabilizer, it is characterised in that by following steps system
:
(1) it takes the tong ma anhydride of 82.01 g to be dissolved in the tetrahydrofuran of 82.01 g, is added in reaction vessel, be warming up to 45
℃；10.81 g p-phenylenediamine are dissolved in the tetrahydrofuran of 200 g, are added dropwise in reaction vessel, 45 after being added dropwise
DEG C reaction 5 h, revolving, vacuum drying obtain product liquid N- (2- aminophenyl) paulownia horse amic acid (APTMA)；
(2) by 0.05 mol N- (2- aminophenyl) paulownia horse amic acid and etc. the diethylene glycol monobutyl ethers of quality be added to reaction vessel
In, it is warming up to 75 DEG C；Until completely dissolved, in two batches or more batches addition 0.047 mol zinc oxide or calcium hydroxide, heating
To 110 DEG C, the glacial acetic acid or hydrogen peroxide for accounting for N- (2- aminophenyl) paulownia horse amide acid mass fraction 0.65% is added dropwise, keeps the temperature 4 h, takes out
Filter, revolving water removal obtain liquid N- (2- aminophenyl) paulownia horse amic acid zinc salt (APTMA-Zn) or N- (2- aminophenyl) paulownia horse amide
Acid calcium salt (APTMA-Ca)；
(3) 8 g N- (2- aminophenyl) paulownia horse amide acid calcium salt is compounded with 2 g N- (2- aminophenyl) paulownia horse amic acid zinc salt,
Obtain liquid composite thermal stabilizer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611203603.7A CN106800670B (en) | 2016-12-23 | 2016-12-23 | Tung oil base binary amic acid calcium-zinc composite liquid heat stabilizer and its preparation method and application |
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|---|---|---|---|
| CN201611203603.7A CN106800670B (en) | 2016-12-23 | 2016-12-23 | Tung oil base binary amic acid calcium-zinc composite liquid heat stabilizer and its preparation method and application |
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| CN106800670B true CN106800670B (en) | 2019-05-03 |
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| CN111793198A (en) * | 2020-06-19 | 2020-10-20 | 广东鑫达新材料科技有限公司 | Calcium salt suitable for PVC calcium zinc stabilizer and preparation method thereof |
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| "Synthesis of the complex of lanthanum (III) with N-(2-amino ethyl) maleamic acid radical and its application to PVC as thermal stabilizer";Miao Li等;《Polymer Degradation and Stability》;20151217;第124卷;第87-94页 |
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