CN105542223B - A kind of preparation method of overbased alkaline earth carboxylate microemulsions - Google Patents
A kind of preparation method of overbased alkaline earth carboxylate microemulsions Download PDFInfo
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- CN105542223B CN105542223B CN201510899921.0A CN201510899921A CN105542223B CN 105542223 B CN105542223 B CN 105542223B CN 201510899921 A CN201510899921 A CN 201510899921A CN 105542223 B CN105542223 B CN 105542223B
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- 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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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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Abstract
The invention discloses a kind of preparation methods of overbased alkaline earth carboxylate microemulsions.Current high alkalinity metal carboxylate changes via induced by alkyl hydroxybenzene to no nonylphenol class, but product is still not sufficiently stable and environmental protection.In the presence of a hydrocarbon solvent, alkali salt is reacted the present invention with carboxylic acid mixing, is acted on by surfactant and long-chain fatty alcohol, forms alkaline earth metal carboxylation's microemulsion precursor of low alkalinity, the wherein molar ratio of alkali salt and carboxylic acid is more than 1:1, there are excessive alkali salts in guarantee system；Under short-chain polyol effect, alkaline earth metal carboxylation's microemulsion precursor carries out carbonation reaction, promote excessive alkali salt to participate in carbonation reaction, so that alkaline earth metal carboxylation's microemulsion precursor of low alkalinity is carbonated and be in neutrality, overbased alkaline earth carboxylate microemulsions are made.Product prepared by the present invention has excellent color keep performance, low plate-out and performance steady in a long-term, has excellent compatibility with liquid stabilisers component.
Description
Technical field
The present invention relates to PVC auxiliary agents, specifically a kind of overbased alkaline earth carboxylate microemulsions (especially carboxylic acid
Barium) preparation method.
Background technology
Overbased alkaline earth carboxylate is prepared using alkylphenol and its derivative（Such as carboxylic salt）It is disclosed following U.S.
State's patent No.：2760970,2767164,2798852,2802816,031284,3342733,3533975,3773664,
3779992,4665117,5830935 and 5859267.These overbased alkaline earth carboxylates are in halogen-containing organic polymer
In purposes be described in United States Patent (USP) 4159973,3294823 and 4252698.
United States Patent (USP) 4665117 uses alkyl phenol as accelerating agent, prepares overbased alkaline earth carboxylate, but make
Metachromatism can occur in PVC stabilizer for standby alkaline earth metal carboxylation, limit the application field of product.United States Patent (USP) 5,
322,872；2,669,549；4,123,399；5,102,933 also pass through complexing agent ketoxime, phosphorous acid, polyalcohol, aromatic series cyanogen
Compound etc. handles alkali metal salt, inhibits product discoloration；However, in recent years in Europe, Asia and American States, with environmental law
It constantly updates, phenol and phenol derivatives have become limitation substance, forbid to occur in chemicals.Therefore, new one is developed
It is extremely urgent for no phenol liquid high alkalinity metal carboxylate.
Chinese patent CN103328425 disclose it is a kind of using beta-diketon as reaction promoter substitution alkylphenol preparation
Go out the method for high alkalinity metal carboxylate.Beta-diketon can participate in neutralization reaction as reactant together with carboxylic acid, form diketone
Hydrochlorate and carboxylate, beta-diketon can be used as accelerating agent to form high alkalinity metal carboxylic acid with industrial speed response during carbonating
Salt.However, beta-diketon itself is also a kind of complexing agent, it is easy to occur with the impurity iron ion in system when it is as accelerating agent
Phenomenon is complexed, product is caused to redden.
The above is the Recent Research of overbased alkali metal carboxylate, passes through being continually striving to for researcher, high alkalinity
Metal carboxylate changes via induced by alkyl hydroxybenzene to no nonylphenol class, but to meet the application and environmental requirement of PVC product, still needs to
It constantly brings forth new ideas, optimize, prepare more stable, environmental protection overbased alkaline earth carboxylate.
Invention content
The technical problem to be solved by the present invention is to overcome the problems of the above-mentioned prior art, one kind is provided completely not
Under conditions of alkylphenol, overbased alkaline earth carboxylic acid is prepared by surfactant and short-chain polyol accelerating agent
The method of salt microemulsion.
For this purpose, the present invention adopts the following technical scheme that：A kind of preparation side of overbased alkaline earth carboxylate microemulsions
Method comprising following steps：
1) in the presence of a hydrocarbon solvent, alkali salt is reacted with carboxylic acid mixing, passes through surfactant and long-chain fat
Fat alcohol acts on, and forms alkaline earth metal carboxylation's microemulsion precursor of low alkalinity, the molar ratio of wherein alkali salt and carboxylic acid is big
In 1:1, there are excessive alkali salts in guarantee system；
2) under short-chain polyol effect, alkaline earth metal carboxylation's microemulsion precursor carries out carbonation reaction, promotes excess
Alkali salt participate in carbonation reaction, make low alkalinity alkaline earth metal carboxylation's microemulsion precursor carbonate be in neutrality, make
Overbased alkaline earth carboxylate microemulsions, the content of alkaline-earth metal is in 30-40% in the microemulsion.
There are excessive metal salts in guarantee system of the present invention, are established for the preparation of overbased alkaline earth carboxylate microemulsions
Fixed basis.Using surfactant and long-chain fatty alcohol, such as fatty acid sorbitan class surfactant so that the first stage is excessive
When alkali salt and carboxylic acid reaction, stable Reverse Microemulsion System is formed, promotes the reverse phase glue for containing a large amount of W/O in system
Beam, excessive alkali salt can slowly be entered inside micella by diffusion, further increase alkaline earth metal content.
In carbonation, by the way that short-chain polyol, such as triethylene glycol substance is added, promote carbon dioxide, alkaline-earth metal
It diffuses into inside micella, to be stablized, runny overbasic alkaline earth metal carboxylation's microemulsion.
Further, the hydrocarbon solvent is preferably C16-C31Positive isoparaffin mixture, it is excellent such as D100, D80, D60 white oil
Select D100 white oils.
Further, the carboxylic acid is preferably aliphatic acid or aromatic carboxylic acid；The aliphatic acid is preferably C8-C20Fat
Acid；The aromatic carboxylic acid is preferably benzoic acid or benzoic acid derivative；The carboxylic acid is most preferably oleic acid, neodecanoic acid, benzene
The mixed acid of one or more of formic acid.
Further, the alkali salt is preferably calcium, barium, magnesium or zinc salt, and most preferably (it contains barium salt in the product
Amount is up to 35%).
Further, the surfactant is preferably fatty acid sorbitan class or poly yamanashi esters surfactant, most
Preferably Span-60；The long-chain fatty alcohol is the fatty alcohol that carbon atom number is more than 12, most preferably isomerous tridecanol；Institute
The short-chain polyol stated is preferably the mixture of one or more of propylene glycol, butanediol, triethylene glycol, dipropylene glycol.
The method of the present invention can be promoted under conditions of being completely absent alkylphenol by surfactant and polyalcohol
Desired overbased alkaline earth carboxylate microemulsions are prepared in agent；And product stable storing obtained, it easily flows, grain size control
System has the preferable transparency in 100 microns.
Overbased alkaline earth carboxylate microemulsions prepared by the present invention have excellent color keep performance, low plate-out
With performance steady in a long-term, there is excellent compatibility with liquid stabilisers component；Meanwhile overbased alkaline earth carboxylic acid of the invention
Salt microemulsion satisfaction Europe and Asian countries are safe to use, environmentally friendly about the requirement for being forbidden to use phenol and phenol derivatives.
These advantages and other advantages and novel feature and embodiment details shown in it that the present invention has will
Become more fully understand from following explanation.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment contributes to those skilled in the art
The present invention is further understood, but these embodiments are not considered as limitation of the scope of the invention.Unless the following examples and
Description and claims elsewhere in it is indicated otherwise, otherwise whole scores and percentage are unit of weights, whole temperature
It is degree Celsius.
In embodiment in the present invention, is acted on by surfactant and long chain fatty acids, form the alkali of low alkalinity
Earth metal carboxylate microemulsions carry out carbonation reaction and are promoted micro- by the facilitation of short-chain polyol on this basis
Lotion carries out acidification reaction, obtains the overbased alkaline earth carboxylate microemulsions of high expectation value, and system has preferable storage
Stability and mobility.
Embodiment 1
By 28.2g oleic acid, 4.3g neodecanoic acids, 33.0g white oil D-100,10.0g isomerous tridecanols and 1.0gSpan-60 tables
The mixture of face activating agent is fitted into reaction vessel, is being stirred and is being warming up to 85 DEG C under nitrogen atmosphere, 20-30min.At 85 DEG C
Under, 23.62g, 23.62g and 23.62g barium monohydrate is added into container in three times, each feeding interval 30min waits for hydrogen
Barium monoxide all adds, and system heats up, and is first warming up to 100 DEG C, controls the water content in 30min or so, observation system, then
135 DEG C of progress second dehydration processing are warming up to, extra water, makes system be in uniform oil phase state in removing system.Substantially
By 1h or so, the Free water in system removes completely, and product is in milky state.Then accelerating agent three is added dropwise into system
Glycol 3.5g is passed through carbon dioxide gas into system after completion of dropwise addition with 1 liter/min of speed, while reducing blowing for nitrogen
Rate is swept, mixture is about carbonated 1.5 hours, system becomes translucent milk yellow, and product has preferable mobility.Anti-
During answering process, water 9g is removed, obtained product is titrated by alkali metal and tested, and barium tenor is 32.3%.
Embodiment 2
28.2g oleic acid, 3.1g benzoic acid, 33.0g white oils D-80,12.0g 12-14 alcohol and the surfaces 1.0gSpan-60 are lived
Property agent mixture be fitted into reaction vessel, stir and nitrogen atmosphere under be warming up to 85 DEG C, 20-30min.At 85 DEG C, point
23.62g, 23.62g and 23.62g barium monohydrate is added into container three times, each feeding interval 30min waits for hydroxide
Barium all adds, and system heats up, and is first warming up to 100 DEG C, controls the water content in 30min or so, observation system, then heat up
To 135 DEG C of progress second dehydration processing, extra water, makes system be in uniform oil phase state in removing system.Substantially pass through
1h or so, the Free water during system is complete remove completely, and product is in milky state.Then accelerating agent third is added dropwise into system
Glycol 3.5g is passed through carbon dioxide gas into system after completion of dropwise addition with 1 liter/min of speed, while reducing blowing for nitrogen
Rate is swept, mixture is about carbonated 1.5 hours, system becomes translucent milk yellow, and product has preferable mobility.Anti-
During answering process, water 8.7g is removed, obtained product is titrated by alkali metal and tested, and barium tenor is 29.3%.
Embodiment 3
With embodiment 2, surfactant is changed to each 0.5g of mixture of Span-60 and Tween-60, accelerating agent the third two
Alcohol is changed to dipropylene glycol, and other conditions are constant, by carbonation reaction, barium metal in the high alkalinity carboxylic acid barium microemulsion of preparation
Content is 34.2%.
Embodiment 4
28.2g isooctyl acids, 4.3g neodecanoic acids, 33.0g white oil D-60,12.0g lauryl alcohols and the surfaces 1.0gSpan-60 are lived
Property agent mixture be fitted into reaction vessel, stir and nitrogen atmosphere under be warming up to 85 DEG C, 20-30min.At 75 DEG C, point
7.4g, 7.4g and 8.0g calcium hydroxide is added into container three times, each feeding interval 30min waits for that calcium hydroxide all adds,
System heats up, and is first warming up to 100 DEG C, controls the water content in 30min or so, observation system, then be warming up to 130 DEG C of progress
Second dehydration is handled, and extra water, makes system be in uniform oil phase state in removing system.Substantially pass through 1h or so, system
Free water in completely removes completely, and product is in milky state.Then accelerating agent triethylene glycol 3.5g, drop are added dropwise into system
Carbon dioxide gas is passed through into system with 1 liter/min of speed after adding, while reducing the purge rates of nitrogen, will be mixed
It closes object about to carbonate 1.5 hours, system becomes translucent faint yellow, and product has preferable mobility.During reaction process,
Water 5g is removed, obtained product is titrated by alkali metal and tested, and calcium tenor is 10.3%.
Embodiment 5
By 28.2g oleic acid, 4.3g neodecanoic acids, 33.0g white oil D-80,12.0g isomerous tridecanols and the surfaces 1.0gSpan-60
The mixture of activating agent is fitted into reaction vessel, is being stirred and is being warming up to 85 DEG C under nitrogen atmosphere, 20-30min.At 80 DEG C,
7.4g, 7.4g and 8.0g calcium hydroxide is added into container in three times, each feeding interval 30min waits for that calcium hydroxide all adds
Complete, system heats up, and is first warming up to 100 DEG C, controls the water content in 30min or so, observation system, then be warming up to 130 DEG C
Second dehydration processing is carried out, extra water, makes system be in uniform oil phase state in removing system.Substantially pass through 1h or so,
Free water during system is complete removes completely, and product is in milky state.Then accelerating agent butanediol is added dropwise into system
4.0g is passed through carbon dioxide gas into system after completion of dropwise addition with 1 liter/min of speed, while reducing the purging speed of nitrogen
Rate about carbonates mixture 1.5 hours, and system becomes translucent faint yellow, and product has preferable mobility.It was reacting
During journey, 4.5 g of water is removed, obtained product is titrated by alkali metal and tested, and calcium tenor is 9.2%.
Embodiment 6
By the mixed of 28.2g oleic acid, 33.0g white oil D-100,12.0g isomerous tridecanols and 1.0gSpan-60 surfactants
It closes object to be fitted into reaction vessel, is stirring and be warming up to 65 DEG C, about 30min under nitrogen atmosphere.At 90 DEG C, in three times to appearance
5.8g, 5.8g and 5.8g magnesium hydroxide are added in device, each feeding interval 30min waits for that magnesium hydroxide all adds, and system carries out
Heating is first warming up to 100 DEG C, controls the water content in 30min or so, observation system, then is warming up to 135 DEG C of progress second dehydrations
It handles, extra water, makes system be in uniform oil phase state in removing system.Substantially pass through 1h or so, during system is complete
Free water removes completely, and product is in milky state.Then accelerating agent dipropylene glycol 3.5g, completion of dropwise addition are added dropwise into system
Carbon dioxide gas is passed through into system with 1 liter/min of speed afterwards, while reducing the purge rates of nitrogen, about by mixture
Carbonating 1.5 hours, system become translucent milk yellow, and product has preferable mobility.During reaction process, water is removed
4.5 g, obtained product are titrated by alkali metal and are tested, and magnesium tenor is 4.3%.
Embodiment 7
14.4g isooctyl acids, 4.3g neodecanoic acids, 30.0g white oil D-60,12.0g isodecanols and the surfaces 1.0gSpan-60 are lived
Property agent mixture be fitted into reaction vessel, stir and nitrogen atmosphere under be warming up to 90 DEG C, 20-30min.At 95 DEG C, point
8.1g, 8.1g and 8.1g zinc oxide, each feeding interval 30min is added into container three times, zinc to be oxidized all adds, system
It heats up, is first warming up to 100 DEG C, control water content in 30min or so, observation system, then to be warming up to 145 DEG C of progress secondary
Dehydration, extra water, makes system be in uniform oil phase state in removing system.Substantially pass through 1h or so, system is complete
In Free water remove completely, product is in milky state.Then accelerating agent propylene glycol 3.5g is added dropwise into system, knot is added dropwise
Carbon dioxide gas is passed through into system with 1 liter/min of speed after beam, while reducing the purge rates of nitrogen, by mixture
It about carbonates 1.5 hours, system becomes translucent milk yellow, and product has preferable mobility.During reaction process, remove
3.5 g of water, obtained product are titrated by alkali metal and are tested, and zinc tenor is 20.8%.
Claims (5)
1. a kind of preparation method of overbased alkaline earth carboxylate microemulsions comprising following steps：
1) in the presence of a hydrocarbon solvent, alkali salt is reacted with carboxylic acid mixing, passes through surfactant and long-chain fatty alcohol
Effect forms alkaline earth metal carboxylation's microemulsion precursor of low alkalinity, and the wherein molar ratio of alkali salt and carboxylic acid is more than 1:
1, there are excessive alkali salts in guarantee system；
2) under short-chain polyol effect, alkaline earth metal carboxylation's microemulsion precursor carries out carbonation reaction, promotes excessive alkali
Earth metal salt participates in carbonation reaction, so that alkaline earth metal carboxylation's microemulsion precursor of low alkalinity is carbonated and is in neutrality, height is made
Basic alkaline earth metal carboxylate microemulsions, the content of alkaline-earth metal is in 30-40% in the microemulsion；
The short-chain polyol is the mixing of one or more of propylene glycol, butanediol, triethylene glycol, dipropylene glycol
Object；The long-chain fatty alcohol is isomerous tridecanol；The surfactant is Span-60；The alkali salt is
Barium salt.
2. preparation method according to claim 1, which is characterized in that the hydrocarbon solvent is C16-C31Positive isoparaffin is mixed
Close object.
3. preparation method according to claim 1, which is characterized in that the carboxylic acid is aliphatic acid or aromatic carboxylic acid.
4. preparation method according to claim 3, which is characterized in that the aliphatic acid is C8-C20Aliphatic acid, it is described
Aromatic carboxylic acid be benzoic acid or benzoic acid derivative.
5. preparation method according to claim 3, which is characterized in that the carboxylic acid is in oleic acid, neodecanoic acid, benzoic acid
One or more kinds of mixed acid.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1671786A (en) * | 2002-07-08 | 2005-09-21 | 克鲁普顿公司 | Overbased metal carbonate/carboxylate microemulsions and halogen-containing polymers containing same |
| CN1894323A (en) * | 2003-11-12 | 2007-01-10 | 科聚亚公司 | Liquid microemulsion stabilizer composition for halogen-containing polymers |
| CN101190881A (en) * | 2006-11-22 | 2008-06-04 | 杭州三叶助剂有限公司 | Special-purpose metal organic salt monomer for liquid stabilizer and preparation method thereof |
| CN103328425A (en) * | 2011-11-29 | 2013-09-25 | 艾姆斯戴比利兹公司 | Process for preparing liquid overbased metal carboxylates, mixed metal stabilizers containing same, and stabilized halogen-containing polymers therewith |
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2015
- 2015-12-09 CN CN201510899921.0A patent/CN105542223B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1671786A (en) * | 2002-07-08 | 2005-09-21 | 克鲁普顿公司 | Overbased metal carbonate/carboxylate microemulsions and halogen-containing polymers containing same |
| CN1894323A (en) * | 2003-11-12 | 2007-01-10 | 科聚亚公司 | Liquid microemulsion stabilizer composition for halogen-containing polymers |
| CN101190881A (en) * | 2006-11-22 | 2008-06-04 | 杭州三叶助剂有限公司 | Special-purpose metal organic salt monomer for liquid stabilizer and preparation method thereof |
| CN103328425A (en) * | 2011-11-29 | 2013-09-25 | 艾姆斯戴比利兹公司 | Process for preparing liquid overbased metal carboxylates, mixed metal stabilizers containing same, and stabilized halogen-containing polymers therewith |
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