CN102076753A - Liquid thermal pvc stabilizers - Google Patents
Liquid thermal pvc stabilizers Download PDFInfo
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- CN102076753A CN102076753A CN2009801260713A CN200980126071A CN102076753A CN 102076753 A CN102076753 A CN 102076753A CN 2009801260713 A CN2009801260713 A CN 2009801260713A CN 200980126071 A CN200980126071 A CN 200980126071A CN 102076753 A CN102076753 A CN 102076753A
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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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
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
PVC thermal liquid stabilizers having no toxicological impact comprising: a) mixed barium and zinc salts of one or more linear or branched aliphatic saturated or unsaturated carboxylic acids containing from 6 to 20 carbon atoms and of one or more aromatic carboxylic acid containing from 8 to 10 carbon atoms, not classified as CRM, wherein the weight ratio of aliphatic acids salts to aromatic acids salts is higher than 3:1; b) one or more organic phosphites of the formula R1OP(OR2)OR3 wherein R1, R2 and R3 are the same or different and each is alkyl containing from 6 to 15 carbon atoms or phenyl or C10-C20 alkylaryl.
Description
Invention field
The present invention relates to be used for the heat of liquid stablizer of PVC, this stablizer toxic effects, PVC has stabilization to plastifying, and this stabilization is similar to the stabilization that use obtains based on the stablizer of the component that carinogenicity, genotoxicity and mutagenicity (CRM) risk is arranged itself.
The preparation that is used for the heat of liquid stablizer of plastifying PVC must use the Ba salt of the lipophilicity acid compatible with the physicochemical property of PVC and the specific mixture of Zn salt; Said preparation also must can provide fitting lubrication when mixing with PVC, make to come processing PVC by the major technique that fluid or softening PVC contact with the thermometal device of machine (calendering, injection moulding, extrude etc.) that requires commonly used.
The 4-p t butylbenzoic acid is the main ingredient of these preparations.CRM classification (genotoxicity classification: 2) is included in this acid at present.Therefore, this acid and corresponding salt thereof shall not be applied to the thermo-stabilizer preparation, may discharge them because contain the PVC finished product of these chemical substances, cause endangering the huge potential risk of public health.
And the staff's possibility long-term exposure that relates in preparation stablizer and the PVC finished product is in above-mentioned chemical substance, and their health has the risk of being encroached on.
Therefore, there is such industrial requirement in the conventional formulation at the heat of liquid stablizer that is used for PVC, promptly with acid substitution 4-p t butylbenzoic acid safer and that have the proper characteristics that can give similar stability of plasticized PVC and processing characteristics.
Background technology
Be used at present plasticized PVC the heat of liquid stablizer state-of-the-art preparation mainly based on: based on the Ba/Zn of long chain aliphatic carboxylic acid and aromatic carboxylic acid's combination or the mixture of Ca/Zn salt; The organic derivative of phosphorus; And optional high boiling hydrocarbon and softening agent as thinner.In these mixtures, add co-stabilizer and other additive such as antioxidant, lubricant, softening agent, to improve performance.
Aromatic carboxylic acid's existence is very important, can not influence transparency because aromatic carboxylic acid's salt can improve the priming color of PVC preparation in the course of processing.Phenylformic acid is the simplest aromatic carboxylic acid, but because the lipophilicity of its inorganic salt is poor, may bring the problem of separating out (place-out), mainly is in the calendering operation.
On the contrary, the 4-p t butylbenzoic acid has the optimum physical chemical property that satisfies this technical requirements.
United States Patent (USP) the 5th, 880 is mentioned a kind of heat stabilizer composition No. 189, and said composition provides good wettability for the PVC film, and the water color ink that is applied on this film is had good adhesivity.Disclose according to this patent documentation, when Ba/Zn salt is based on C
8-C
10When (preferred about 1: 1), Ba/Zn heat of liquid stablizer has good performance to the weight ratio of aromatic carboxylic acid and aliphatic carboxylate and aromatic carboxylic acid salt in 3: 1 to 1: 3 scope.
Unexpectedly, we have found that, even the ratio of aliphatic carboxylate and C8-C10 aromatic carboxylic acid salt surpasses 3: 1, also can make thermo-stabilizer have following performance: also noiseless in the preparation to the processing characteristics of the thermally-stabilised ability of stablizer and PVC without the 4-p t butylbenzoic acid.
Summary of the invention
An aspect of of the present present invention is a kind of Ba/Zn liquid stabiliser composition, and said composition does not contain the 4-p t butylbenzoic acid, can give splendid thermostability of PVC and processibility, and does not have the defective of phenylformic acid and salt thereof.
Especially, the main ingredient in this heat of liquid stabilizer formula is:
A) one or more contain the saturated or unsaturated carboxylic acid of the straight or branched aliphatic series of 6-20 carbon atom and one or more contain the aromatic carboxylic acid's of 8-10 carbon atom mixing barium salt and zinc salt, these salt do not belong to the CRM classification, wherein, the weight ratio of aliphatic hydrochlorate and aromatics hydrochlorate is higher than 3: 1;
B) one or more have general formula R
1OP (OR
2) OR
3Organophosphite, R wherein
1, R
2And R
3Be identical or different, respectively do for oneself and contain the alkyl of 6-15 carbon atom, or phenyl, or C
10-C
20Alkylaryl.
Detailed Description Of The Invention
One of most important aspect of heat of liquid stablizer of the present invention is that they can make the operator of plasticized PVC avoid with chemical that has toxicity problem such as genotoxicity product (2 class) any contact being taken place with the terminal user.
In fact, liquid stabilisers of the present invention has avoided belonging to the hydrochlorate of above-mentioned toxicity classification.
This liquid stabilisers is by oxyhydroxide or the oxide compound and the C of barium and zinc
6-C
20Aliphatic carboxylic acid and C
8-C
10Aromatic carboxylic acid's mixture reaction prepares; This salt-forming reaction is randomly at general formula R
1OP (OR
2) OR
3Organophosphite and solvent carry out under existing, described solvent is selected from C
8-C
16Alkyl alcohol, glycol or glycol ethers, or the hydrocarbon of low volatility.Perhaps, general formula R
1OP (OR
2) OR
3Organophosphite and above-mentioned solvent can when salt-forming reaction finishes, add.
Randomly, can in the heat of liquid stablizer of above-mentioned preparation, add one or more co-stabilizers, for example beta-diketon and dihydropyridine, carboxylic acid barium/barium carbonate (high alkalinity barium) solution, C
6-C
20The zinc salt of aliphatic carboxylic acid (on the ratio of Ba/Zn, more flexibility being arranged).Preferably, in heat of liquid stablizer of the present invention, do not add phosphorous acid ester.
Described salt mixture comprises the positively charged ion of Ba and Zn.The weight ratio of Ba/Zn is about 1 in the salt mixture: 1-10: 1, preferably be about 3: 1-8: and 1, be more preferably 3.5: 1 and 4: 1.
Salt mixture also comprises and contains two kinds of dissimilar anionic anionic groups.One type is selected from down negatively charged ion of organizing by one or more and forms: the aliphatic carboxylic acid of straight or branched, the saturated or undersaturated 6-20 of containing carbon atom; Preferred acid is the carboxylic acid that 0-3 carbon-carbon double bond arranged in the molecule.Most preferred carboxylic acid is oleic acid (or sweet oil lipid acid), neodecanoic acid and sad isomer, for example 2 ethyl hexanoic acid.Second anionoid is made up of the aromatic carboxylic acid that one or more contain 8-10 carbon atom.The aromatic carboxylic acid is the molecule that contains phenyl ring, and wherein carboxylic moiety directly or indirectly is connected with phenyl ring by saturated or unsaturated alkylene bridge; Phenyl ring can be replaced by one or more alkyl extraly.Preferred aromatic carboxylic acid is benzoic substitutive derivative; Most preferred aromatic carboxylic acid is the acid of not being included into CRM, especially 4-isopropyl acid, 4-ethyl benzoate, 2-tolyl acid, 3-tolyl acid, 4-tolyl acid, 3,4-mesitylenic acid and mesitylene carboxylic acid.
Aliphatic carboxylate and C
8-C
1The weight ratio of 0 aromatic carboxylic acid salt is higher than 3: 1, preferably in about 3.5: 1 to 7: 1 scope.
Described salt mixture can pass through alkaline Zn and Ba compound such as zinc oxide and hydrated barta and aliphatic carboxylic acid or C
6-C
20Aliphatic carboxylic acid (for example oleic acid, neodecanoic acid or 2 ethyl hexanoic acid) and aromatic carboxylic acid's mixture reacts in the presence of organophosphite and prepares, described aromatic carboxylic acid for example is 4-isopropyl acid, 4-ethyl benzoate, 2-tolyl acid, 3-tolyl acid, 4-tolyl acid, 3,4-mesitylenic acid and 2,4,6-trimethylbenzoic acid or their mixture.This is reflected under the vigorous stirring and carries out, and obtains the homogeneous mixture of organic acid barium salt and zinc salt.
The preparation of thermo-stabilizer also may need to use solvent, for example high boiling hydrocarbon (for example mixture of the hydrogenation naphthenic hydrocarbon of isoparaffin and Exxsol classification), C
12-C
15Oxo alcohol, glycol, glycol ethers, straight chain, side chain C
15-C
40The mixture of alkylbenzene, and their mixture.
General formula R
1OP (OR
2) OR
3Organophosphite be main compound in the heat of liquid stablizer of the present invention, R wherein
1, R
2And R
3Be identical or different, respectively do for oneself and contain the alkyl of 6-15 carbon atom, or phenyl, or C
10-C
20Alkylaryl; Preferred organophosphite is trialkyl phosphite, diphenyl alkyl phosphorous acid ester, phenyl dialkyl phosphorous acid ester, triphenyl phosphorous acid ester, trialkyl aromatic yl phosphite, di alkylaryl alkyl phosphorous acid ester, an alkylaryl dialkyl phosphites, or their mixture; Most preferred organophosphite is three nonyl phenyl phosphites, decyl phenylbenzene phosphorous acid ester and three (tridecyl) phosphorous acid ester.
Organophosphite also can add after above-mentioned salinization reaction.Preferably, organophosphite adds after the salinization reaction, and organophosphite is the mixture of decyl phenylbenzene phosphorous acid ester and/or three (tridecyl) phosphorous acid ester and/or trialkyl phosphite (5-9%), dialkyl group nonyl phenyl phosphites (42-43%) and an alkyl dinonyl phenyl phosphites+three nonyl phenyl phosphites (53-48%), and wherein alkyl is straight chain or the single branched-chain alkyl that contains 12-15 carbon atom.
The gross weight of phosphorous acid ester (representing) and Ba and Zn mixing salt with P the ratio of weight be 0.04-0.07, more preferably 0.05-0.06.
Can be under suitable temperature; under agitation in the mixture that obtains like this, add one or more co-stabilizers; for example beta-diketon or dihydropyridine are more preferably phenyl phenacyl ketone, stearyl-benzoyl methane, dehydroacetic acid (DHA) or their mixture.
Gross weight in stablizer is a benchmark, and the add-on of co-stabilizer is 0.1 weight %-8 weight %, is preferably 0.2 weight %-5 weight %, more preferably 0.4 weight %-3 weight %.
Other component that can join in the thermo-stabilizer preparation is: C
6-C
20The high alkalinity barium of aliphatic carboxylic acid, zinc salt, other additive such as antioxidant, softening agent, lubricant, fire retardant, filler, pigment etc., their relative quantity should satisfy the required function of each annexing ingredient.These components can add after the mixture of preparation salt and phosphorous acid ester.
Effectively the Reinforced PVC resin is to the tolerance of heating agent deterioration (heat-mediateddeterioration) for stabiliser system of the present invention, and the heating agent deterioration is just owing to the deterioration of excessively being heated and causing, and the deterioration that causes or accelerate owing to being heated.
In the literary composition used term " PVC " comprise to small part by recurring group (CHCl-CX
2-)
nFormation and cl content surpass any polymkeric substance of 40%.In this general formula, each X group can be hydrogen or chlorine, and n is the unit number of polymer chain.In the PVC homopolymer, each X group is a hydrogen.Therefore, this term not only comprises polyvinyl chloride homopolymer, the polyvinyl chloride that also comprises post chlorization, and vinylchlorid is as the multipolymer of main ingredient and other copolymerisable monomer, the multipolymer of vinylchlorid and vinyl-acetic ester for example, the multipolymer of vinylchlorid and toxilic acid or fumaric acid or its ester, and vinylchlorid and cinnamic multipolymer.
Stabiliser composition of the present invention also is effective for the PVC mixture of other synthetic resins of PVC that contains main ratio and minor proportions (for example chlorinatedpolyethylene or vinyl cyanide, divinyl and styrol copolymer).
Stablizing plastifying PVC during stabiliser composition of the present invention preferably can be used on different manufacturing process such as calendering, injection moulding, extrude etc., is effective especially in calendering technology.
Their consumption is less, but can give PVC the stability of required opposing heating agent deterioration effectively.Can realize effective thermostability by the thermo-stabilizer of the present invention that in polyvinyl chloride resin, adds about 1-5phr (parts by weight/100 parts by weight resin).The amount of stablizer preferably is about 1.5-3phr.
Following examples are used for illustrating the preparation and the application of stablizer of the present invention.The purpose of following examples is to be used for explanation, and the scope of the present invention that unrestricted applicant thinks.
Embodiment 1-uses the 4-ethyl benzoate
With 97.5 gram oleic acid, 17.5 gram 4-thylhexoic acids, 44.5 gram oxo alcohol C
12-C
15, 5.9 gram linear alkylbenzene C
15-C
40Mix in the round-bottomed flask of heating with 67.0 grams, three nonyl phenyl phosphites, and stir with mechanical stirrer.
This mixture 60 ℃ of heating, is added 12.0 gram zinc oxide in batches.Temperature is elevated to 100 ℃.After 1 hour, add 33.1 gram 4-ethyl benzoates and 36 gram dried barium hydroxides.Temperature is elevated to 140 ℃, kept 2 hours in this temperature.Obtain the clarified mixture of 300 gram Ba salt and Zn salt, the weight ratio of Ba/Zn is 2.7: 1.
At 60 ℃, under agitation in this mixture, add 94.7 gram decyl phenylbenzene phosphorous acid esters, 63.2 and restrain the solution of zinc salts (Zn content is 2.1 grams) formation in decyl phenylbenzene phosphorous acid ester (13.8 gram) of high alkalinity barium salts (barium content is 17.7 grams), 26.3 gram oleic acid and neodecanoic acid, mixture, 10 gram phenyl phenacyl ketones and the 10 gram antioxidants of 22.1 gram linear alkylbenzene C15-C40.
Obtain 526.3 gram Ba/Zn stablizers, wherein the ratio of Ba/Zn is 3.7: 1, and the ratio of aliphatic carboxylic acid and 4-ethyl benzoate is 4.16: 1.Ratio between the weight of the total content of phosphorus and Ba salt and Zn salt is 0.051.
Embodiment 2-uses the 4-isopropyl acid
Repeat the step of embodiment 1, but the 4-ethyl benzoate is replaced by 36.2 gram 4-isopropyl acids, with linear alkylbenzene C
15-C
40Amount reduce to 2.8 the gram.
Obtain 526.3 gram Ba/Zn stablizers, wherein the ratio of Ba/Zn is 3.7: 1, and the ratio of aliphatic carboxylic acid and 4-isopropyl acid is 3.8: 1.Ratio between the weight of the total content of phosphorus and Ba salt and Zn salt is 0.051.
Embodiment 3 (using the 4-tolyl acid)
Repeat the step of embodiment 1, but the 4-ethyl benzoate is replaced by 30.0 gram 4-tolyl acids, with linear alkylbenzene C
15-C
40Amount be increased to 9.0 the gram.
Obtain 526.3 gram Ba/Zn stablizers, wherein the ratio of Ba/Zn is 3.7: 1, and the ratio of aliphatic carboxylic acid and 4-tolyl acid is 4,6: 1.Ratio between the weight of the total content of phosphorus and Ba salt and Zn salt is 0.052.
Embodiment 4 (using the 3-tolyl acid)
Repeat the step of embodiment 1, but the 4-ethyl benzoate is replaced by 30.0 gram 3-tolyl acids, with linear alkylbenzene C
15-C
40Amount be increased to 9.0 the gram.
Obtain 526.3 gram Ba/Zn stablizers, wherein the ratio of Ba/Zn is 3.7: 1, and the ratio of aliphatic carboxylic acid and 3-tolyl acid is 4.6: 1.Ratio between the weight of the total content of phosphorus and Ba salt and Zn salt is 0.052.
Embodiment 5 (using the 2-tolyl acid)
Repeat the step of embodiment 1, but the 2-ethyl benzoate is replaced by 30 gram 2-tolyl acids, with linear alkylbenzene C
15-C
40Amount be increased to 9.0 the gram.
Obtain 526.3 gram Ba/Zn stablizers, wherein the ratio of Ba/Zn is 3.7: 1, and the ratio of aliphatic carboxylic acid and 2-tolyl acid is 4.6: 1.Ratio between the weight of the total content of phosphorus and Ba salt and Zn salt is 0.052.
Embodiment 6 (using 3, the 4-mesitylenic acid)
Repeat the step of embodiment 1, but the 4-ethyl benzoate is restrained 3 by 33.1, the 4-mesitylenic acid replaces.
Obtain 526.3 gram Ba/Zn stablizers, wherein the ratio of Ba/Zn is 3.7: 1, and aliphatic carboxylic acid and 3, the ratio of 4-mesitylenic acid are 4.16: 1.Ratio between the weight of the total content of phosphorus and Ba salt and Zn salt is 0.051.
Embodiment 7 (use mesitylene carboxylic acid)
Repeat the step of embodiment 1, but the 4-ethyl benzoate is restrained 2,4 by 36.2, the 6-tolyl acid replaces, with linear alkylbenzene C
15-C
40Amount reduce to 2.8 the gram.
Obtain 526.3 gram Ba/Zn stablizers, wherein the ratio of Ba/Zn is 3.7: 1, and the ratio of aliphatic carboxylic acid and mesitylene carboxylic acid is 3.8: 1.Ratio between the weight of the total content of phosphorus and Ba salt and Zn salt is 0.051.
Embodiment 8 (using phenylformic acid product as a comparison)
Repeat the step of embodiment 1, but the 4-ethyl benzoate is replaced by 26.9 gram phenylformic acid, with linear alkylbenzene C
15-C
40Amount be increased to 12.1 the gram.
Obtain 526.3 gram Ba/Zn stablizers, wherein the ratio of Ba/Zn is 3.7: 1, and aliphatic carboxylic acid and benzoic ratio are 5.1: 1.Ratio between the weight of the total content of phosphorus and Ba salt and Zn salt is 0.053.
Embodiment 9 (using 4-p t butylbenzoic acid product as a comparison)
Repeat the step of embodiment 1, but the 4-ethyl benzoate is replaced by 39.3 gram 4-p t butylbenzoic acids, does not use linear alkylbenzene C
15-C
40, with oxo alcohol C
12-C
15Amount reduce to 44.2 the gram.
Obtain 526.3 gram Ba/Zn stablizers, wherein the ratio of Ba/Zn is 3.7: 1, and aliphatic carboxylic acid and benzoic ratio are 3.5: 1.Ratio between the weight of the total content of phosphorus and Ba salt and Zn salt is 0.050.
Embodiment 10 (use the 3-tolyl acid, the ratio between aliphatic carboxylic acid and the 3-tolyl acid is higher)
With 20 gram oleic acid, 1.8 gram neodecanoic acids, 7.2 gram oxo alcohol C
12-C
15, 10.8 grams, three nonyl phenyl phosphites mix in the round-bottomed flask of heating, and stir with mechanical stirrer.
This mixture 60 ℃ of heating, is added 2.4 gram zinc oxide in batches.Under agitation temperature is elevated to 100 ℃.After 1 hour, in clarified mixture, add 5.1 gram 3-tolyl acids and 5.8 gram dried barium hydroxides.Temperature slowly is elevated to 140 ℃, kept 2 hours in this temperature.Obtain the clarified mixture of 50 gram Ba salt and Zn salt, the weight ratio of Ba/Zn is 2.2: 1.
At 60 ℃, under agitation in this mixture, add mixture, 10 gram diethylene glycol monobutyl ethers, 4 gram phenyl phenacyl ketones and 3 gram phenol antioxidant that 26 gram decyl phenylbenzene phosphorous acid esters, 30 restrain zinc salts (Zn content is 1.6 grams) solution, 57 gram isoparaffins and hydrogenation naphthenic hydrocarbon of formation in decyl phenylbenzene phosphorous acid ester (10.5 gram) of high alkalinity barium salts (barium content is 8.4 grams), 20 gram oleic acid and neodecanoic acid.
Obtain 200 gram Ba/Zn stablizers, wherein the ratio of Ba/Zn is 3.6: 1, and the ratio of aliphatic carboxylic acid and 3-tolyl acid is 6.8: 1.
Ratio between the weight of the total content of phosphorus and Ba salt and Zn salt is 0.059.
Embodiment 11
For the test that the performance of the stablizer of estimating embodiment 1-10 is carried out as described below:
A) static heat stability
In order to carry out the static heat stability test, the stabilizer formulations of putting down in writing in the foregoing description is attached in the polyvinyl chloride resin with prescription shown in the table 1.
Table 1
| Component | Amount (phr) |
| PVC-S?K70 | 100 |
| DIDP | 32 |
| Epoxidised soybean oil | 3 |
| CaCO 3 | 20 |
| TiO 2 | 15 |
The embodiment 1-4,6 of 2.5phr, the stablizer of 10 and 9 (as a comparison) are joined in the uniform mixture of these components; After adding stablizer, handle each mixture with the end runner mill (180 ℃ of temperature, frictional force 1-1.5) of heating.After mixing 3 minutes, obtain the PVC film, after the room temperature cooling, from the bar of some 2x20 centimetres of this film cutting-outs.
These are introduced in 200 ℃ the Werner Mathis baking oven, and be 4 minutes basic time, per 4 minutes 20 millimeters.
After loop ends, from baking oven, take out sample, mark from the starting point of bar to the distance that takes fire (millimeter).
The starting point of bar and the distance that takes fire between the place are long more, and stablizer effective more (table 2) is described.
Table 2
| Stablizer | Millimeter |
| Embodiment 1 | 190 |
| Embodiment 2 | 185 |
| Embodiment 3 | 190 |
| Embodiment 4 | 185 |
| Embodiment 5 | 180 |
| Embodiment 10 | 180 |
| Embodiment 9 (contrast) PTBBA | 175 |
B) separate out (plate out): the thermo-stabilizer preparation of putting down in writing in the foregoing description is attached in the polyvinyl chloride resin with prescription shown in the table 3.
Table 3
The stablizer that in the uniform mixture of these components, adds the embodiment 1-7 and 8 (as a comparison) of 2phr; After adding stablizer, handled each mixture 1 minute with the end runner mill (180 ℃ of right cylinder temperature, frictional force 1-1.5) of heating.
Then, under unclean cylindrical situation, take out sheet.
Formulation preparation cleaning mixt with table 4.
Table 4
| Component | Amount (phr) |
| ?PVC-S?K70 | 100 |
| ?DOP | 40 |
| ?CaCO 3 | 20 |
| ?TiO 2 | 1 |
| Stablizer | 2 |
The gel on end runner mill of this cleaning mixt mixed 3 minutes continuously at 180 ℃ on right cylinder.When finishing, sheet is separated from right cylinder.The color of sheet is dense more, illustrates that the amount of the material that former preparation stays is many more.With the color of colorimeter evaluation cleaning foil, measure a
*Value can quantize the relative difference between the variant production in this manner.a
*Be worth high more, illustrate separate out serious more.
Table 5
| Stablizer | a * |
| Embodiment 1 | 3.68 |
| Embodiment 2 | 4.09 |
| Embodiment 3 | 4.56 |
| Embodiment 4 | 6.09 |
| Embodiment 5 | 7.38 |
| Embodiment 6 | 3.88 |
| Embodiment 7 | 10.28 |
| Embodiment 8 (contrast, phenylformic acid) | 17.50 |
The foregoing description shows, uses aromatic carboxylic acid C
8-C
10The stablizer of preparation has following feature:
A) compare the stability that has identical opposing PVC thermal degradation when at least with using the 4-p t butylbenzoic acid, they can replace threatening the 4-p t butylbenzoic acid of public health like this;
B) compare with phenylformic acid and reduced separating out in the PVC sheet course of processing, particularly use for calendering, this effect is extremely important in industrial practice.
Claims (10)
1. heat of liquid stablizer that is used for PVC, it comprises:
A) one or more contain the saturated or unsaturated carboxylic acid of the straight or branched aliphatic series of 6-20 carbon atom and one or more contain the aromatic carboxylic acid's of 8-10 carbon atom mixing barium salt and zinc salt, these salt do not belong to the CRM classification, wherein, the weight ratio of aliphatic hydrochlorate and aromatics hydrochlorate is higher than 3: 1;
B) one or more have general formula R
1OP (OR
2) OR
3Organophosphite, R wherein
1, R
2And R
3Be identical or different, respectively do for oneself and contain the alkyl of 6-15 carbon atom, or phenyl, or C
10-C
20Alkylaryl.
2. the heat of liquid stablizer that is used for PVC as claimed in claim 1 is characterized in that this stablizer also comprises one or more co-stabilizers, and it is selected from beta-diketon, dihydropyridine, carboxylic acid barium/barium carbonate (high alkalinity barium) solution, C
6-C
20The zinc salt of aliphatic carboxylic acid.
3. as each described heat of liquid stablizer that is used for PVC in the above-mentioned claim, it is characterized in that the weight ratio of aliphatic carboxylate and aromatic carboxylic acid salt is about 3.5: 1 to 7: 1.
4. as each described heat of liquid stablizer that is used for PVC in the above-mentioned claim, it is characterized in that the weight ratio of Ba/Zn is about 1: 1 to 10: 1.
5. the heat of liquid stablizer that is used for PVC as claimed in claim 4 is characterized in that the weight ratio of Ba/Zn is about 3: 1 to 8: 1.
6. the heat of liquid stablizer that is used for PVC as claimed in claim 5 is characterized in that the weight ratio of Ba/Zn is about 3.5: 1 and 4: 1.
7. the heat of liquid stablizer that is used for PVC as claimed in claim 1, it is characterized in that, aliphatic carboxylic acid is selected from oleic acid (or sweet oil lipid acid), neodecanoic acid or 2 ethyl hexanoic acid, aromatic acid is selected from 4-isopropyl acid, 4-ethyl benzoate, 2-tolyl acid, 3-tolyl acid, 4-tolyl acid, 3,4-mesitylenic acid and 2,4, the 6-trimethylbenzoic acid.
8. the heat of liquid stablizer that is used for PVC as claimed in claim 7, it is characterized in that organophosphite is selected from trialkyl phosphite, diphenyl alkyl phosphorous acid ester, phenyl dialkyl phosphorous acid ester, triphenyl phosphorous acid ester, trialkyl aromatic yl phosphite, di alkylaryl-alkyl phosphorous acid ester, one alkylaryl-dialkyl phosphites.
9. the heat of liquid stablizer that is used for PVC as claimed in claim 8 is characterized in that, the gross weight of phosphorous acid ester (representing) and Ba and Zn mixing salt with P the ratio of weight be 0.04-0.07.
10. as each described application that is used for the heat of liquid stablizer of PVC in plasticized PVC calendering operation among the claim 1-9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITVA2008A000038 | 2008-06-30 | ||
| IT000038A ITVA20080038A1 (en) | 2008-06-30 | 2008-06-30 | LIQUID THERMAL STABILIZERS FOR PVC |
| PCT/EP2009/058174 WO2010000734A1 (en) | 2008-06-30 | 2009-06-30 | Liquid thermal pvc stabilizers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102076753A true CN102076753A (en) | 2011-05-25 |
Family
ID=40302238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801260713A Pending CN102076753A (en) | 2008-06-30 | 2009-06-30 | Liquid thermal pvc stabilizers |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2294122A1 (en) |
| CN (1) | CN102076753A (en) |
| IT (1) | ITVA20080038A1 (en) |
| RU (1) | RU2010151127A (en) |
| WO (1) | WO2010000734A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317453B (en) * | 2015-07-10 | 2018-10-26 | 奕益实业有限公司 | Liquid phosphorus-containing stabilizers and its preparation method |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219926A (en) * | 2011-04-18 | 2011-10-19 | 浙江海普顿化工科技有限公司 | Zinc base liquid composite heat stabilizer and preparation method of zinc base liquid composite heat stabilizer |
| WO2014028943A1 (en) | 2012-08-17 | 2014-02-20 | Metabolix, Inc. | Biobased rubber modifiers for polymer blends |
| US10669417B2 (en) | 2013-05-30 | 2020-06-02 | Cj Cheiljedang Corporation | Recyclate blends |
| JP6811006B2 (en) * | 2015-05-26 | 2021-01-13 | 協同油脂株式会社 | Hydrogen bond aggregates and lubricant compositions containing the aggregates |
| CN106084538B (en) * | 2016-06-14 | 2018-10-30 | 浙江海普顿新材料股份有限公司 | A kind of liquid carboxylic metal salt and the preparation method and application thereof |
| CN106084810A (en) * | 2016-08-26 | 2016-11-09 | 江苏联盟化学有限公司 | A kind of high-performance PVC (polyvinyl chloride) liquid composite thermal stabilizer |
| CN106751213B (en) * | 2016-12-26 | 2018-11-27 | 中国林业科学研究院林产化学工业研究所 | PVC grease source sodium/zinc composite liquid heat stabilizer and its preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2204267A1 (en) * | 1994-11-14 | 1996-05-23 | Michael A. Croce | Liquid pvc stabilizers and lubricants |
| AU2002365502A1 (en) * | 2001-11-28 | 2003-06-10 | Akzo Nobel N.V. | Neutral carbonated alkaline earth metal carboxylates |
-
2008
- 2008-06-30 IT IT000038A patent/ITVA20080038A1/en unknown
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2009
- 2009-06-30 RU RU2010151127/05A patent/RU2010151127A/en not_active Application Discontinuation
- 2009-06-30 WO PCT/EP2009/058174 patent/WO2010000734A1/en active Application Filing
- 2009-06-30 CN CN2009801260713A patent/CN102076753A/en active Pending
- 2009-06-30 EP EP09772434A patent/EP2294122A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317453B (en) * | 2015-07-10 | 2018-10-26 | 奕益实业有限公司 | Liquid phosphorus-containing stabilizers and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2294122A1 (en) | 2011-03-16 |
| RU2010151127A (en) | 2012-08-10 |
| WO2010000734A1 (en) | 2010-01-07 |
| ITVA20080038A1 (en) | 2010-01-01 |
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Application publication date: 20110525 |