CN108176326A - A kind of Rosinpolyether sulfonate and preparation method thereof - Google Patents
A kind of Rosinpolyether sulfonate and preparation method thereof Download PDFInfo
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- CN108176326A CN108176326A CN201711335006.4A CN201711335006A CN108176326A CN 108176326 A CN108176326 A CN 108176326A CN 201711335006 A CN201711335006 A CN 201711335006A CN 108176326 A CN108176326 A CN 108176326A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/326—Polymers modified by chemical after-treatment with inorganic compounds containing sulfur
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Abstract
The invention discloses a kind of Rosinpolyether sulfonate and preparation method thereof, the general structure of the Rosinpolyether sulfonate is：Wherein, m is 0~100 integer, and n is 0~100 integer, and is 0 during m with n differences.Preparation method is as follows：First by acrylic acid rosin, propylene oxide and ethylene oxide polymerization, Rosinpolyether copolymer is obtained, then with SO3Sulfonation is carried out to Rosinpolyether copolymer by falling liquid film method for sulfonated reagent, you can obtain Rosinpolyether sulfonate.The present invention prepares Rosinpolyether sulfonate by falling liquid film method, there is sulphonation rate is high, reaction is fast, lighter color, disodium salt are low etc., the Rosinpolyether sulfonate of preparation has excellent surface-active, emulsibility, dispersibility, wetability and good biocompatibility, and it is degradable, it can be applied to the fields such as pesticidal emulsifiable, coating, ink, washing.
Description
Technical field
The present invention relates to a kind of Rosinpolyether sulfonate and preparation method thereof.
Background technology
At present, alkane (virtue) base phenol ether surfactant (APEO) is widely used in the fields such as washing, weaving, coating, special
It does not occupy an leading position in using agriculture breast 600#, 700#, 1600# as the agricultural surfactant of representative (about 80%).However, APEO
Degradation is slow, and catabolite has the function of similar female hormone, can influence human body and the normal hormone secretion of animal body, draw
Play female effect and distortion.Therefore, there is an urgent need to develop the green surfactants that can substitute APEO.
CN 101708443A disclose type double type block polyether sulfonate surfactant and preparation method thereof with
Using first by the activated monomer containing amino, hydroxyl or carboxyl and propylene oxide, ethylene oxide sequential polymerization formation block polyether
Copolymer, then using urea as catalyst, with sulfamic acid sulfonation, obtain hyper-branched block polyether sulfonate high-molecular surface active
Agent.The surfactant has good dispersion and emulsion stability, has good application prospect in fields such as pesticide, coating,
But it needs to carry out sulfonation using sulfamic acid in preparation process, and by-product is more, and sulfonation degree is low, and more difficult purification.
Rosin-based surfactant is using rosin as raw material, and obtained green surface is synthesized from different hydrophilic radical reactions
Activating agent.Rosin-based surfactant easily biological-degradable, safety and environmental protection, emulsifiability are excellent, dispersion performance and wettability are good,
There is important use in fields such as food, cosmetics, pesticide, coating, ink, papermaking.It is well known that prepare the work of oil primary surface
Property agent needs to consume a large amount of petroleum resources, and rosin is the renewable resource that a kind of source is extremely abundant in nature, so
There is very big advantage compared with oil based surfactants in rosin-based surfactant.
CN 102921349A disclose a kind of disproportionated rosin Ji Yin/nonionic complexed surfactant and preparation method thereof,
Preparation method belongs to one kettle way, and disproportionated rosin and polyethylene glycol is first made to form rosin polyethylene glycol dibasic acid esters, then uses sulphur
The agent concentrated sulfuric acid or chlorosulfonic acid carry out sulfonation to phenyl ring, further into salt, obtain abietyl the moon/nonionic composite surface activity
Agent.However, one kettle way is although easy to operate, it is easy to surfactant product, but the esterification yield of this method just can be prepared
It is low, and need by the use of the concentrated sulfuric acid or chlorosulfonic acid as sulfonating agent, easily lead to that product sulfonation degree is low, and color and luster is deep.
Invention content
The purpose of the present invention is to provide a kind of Rosinpolyether sulfonate and preparation method thereof.
The technical solution used in the present invention is：
A kind of Rosinpolyether sulfonate, general structure are：
Wherein, m is 0~100 integer, and n is 0~100 integer, and is 0 during m with n differences.
The preparation method of above-mentioned Rosinpolyether sulfonate, includes the following steps：
1) synthesis of Rosinpolyether copolymer：By acrylic acid rosin and catalyst mixing, propylene oxide is added in, it is fully anti-
Should, aging adds ethylene oxide, fully reacts, and aging obtains Rosinpolyether copolymer；
2) synthesis of Rosinpolyether sulfonate：Rosinpolyether copolymer solvent is disperseed, then be passed through falling film type from top
Xanthator makes it be flowed down along inner wall, while is passed through from top containing SO3Gaseous mixture, fully react, aging, remove solvent, adjust
PH value is saved, obtains Rosinpolyether sulfonate.
Catalyst described in step 1) is alkali metal hydroxide, one kind of double metal cyanide, bimetallic oxide.
The molar ratio of acrylic acid rosin, catalyst, propylene oxide, ethylene oxide described in step 1) is 1：(0.2~1)：
(40~150)：(60~180).
The molar ratio of propylene oxide, ethylene oxide described in step 1) is (0.3~2)：1.
Reaction described in step 1) carries out under conditions of 120~180 DEG C of temperature, pressure -0.1~1.0MPa.
Rosinpolyether copolymer, SO described in step 2)3Molar ratio be 1：(1~1.7).
The mass ratio of Rosinpolyether copolymer, solvent described in step 2) is 1：(1~5).
Solvent described in step 2) is petroleum ether, n-hexane, ethyl acetate, acetone, methanol, ethyl alcohol, chloroform, dichloromethane
At least one of.
Contain SO described in step 2)3Gaseous mixture in SO3Volume fraction be 1%~6%.
Step 1) and 2) described in aging carried out at 40~90 DEG C, ageing time be 25~70min.
The beneficial effects of the invention are as follows：The present invention prepares Rosinpolyether sulfonate by falling liquid film method, high, anti-with sulphonation rate
It should fast, lighter color, disodium salt be low etc. that advantages, the Rosinpolyether sulfonate of preparation have excellent surface-active, emulsibility, dispersion
Property, wetability and good biocompatibility, and it is degradable, it can be applied to the fields such as pesticidal emulsifiable, coating, ink, washing.
The present invention prepares Rosinpolyether sulfonate using falling liquid film method, with cheap SO3As sulfonating agent, using falling film type sulphur
Makeup is put, and organic matter raw material is uniformly distributed in the reaction tube arranged in tubulation and along under inside pipe wall film-like in reaction process
It falls, contains SO with catadromous3Gaseous mixture contact after sulfonating reaction can occur rapidly compared with traditional process for sulfonation,
Falling film sulfonation units can make organic matter raw material and SO3It comes into full contact with, and due to reactor film-cooled heat and reactor volume ratio
Higher, the Rosinpolyether sulfonate sulphonation rate of synthesis is high, and reaction is fast, lighter color, disodium salt are low.
Description of the drawings
Fig. 1 is the structure diagram of the falling film sulfonation units in the present invention.
Specific embodiment
A kind of Rosinpolyether sulfonate, general structure are：
Wherein, m is 0~100 integer, and n is 0~100 integer, and is 0 during m with n differences.
The synthetic route of above-mentioned Rosinpolyether sulfonate is as follows：
The preparation method of above-mentioned Rosinpolyether sulfonate, includes the following steps：
1) synthesis of Rosinpolyether copolymer：By acrylic acid rosin and catalyst mixing, propylene oxide is added in, it is fully anti-
Should, aging adds ethylene oxide, fully reacts, and aging obtains Rosinpolyether copolymer；
2) synthesis of Rosinpolyether sulfonate：Rosinpolyether copolymer solvent is disperseed, then be passed through falling film type from top
Xanthator makes it be flowed down along inner wall, while is passed through from top containing SO3Gaseous mixture, fully react, aging, remove solvent, adjust
PH value is saved, obtains Rosinpolyether sulfonate.
Preferably, the catalyst described in step 1) is alkali metal hydroxide, double metal cyanide, bimetallic oxide
It is a kind of.
Preferably, the acrylic acid rosin described in step 1), catalyst, propylene oxide, ethylene oxide molar ratio be 1：
(0.2~1)：(40~150)：(60~180).
Preferably, the propylene oxide described in step 1), ethylene oxide molar ratio be (0.3~2)：1.
Preferably, the reaction described in step 1) carries out under conditions of 120~180 DEG C of temperature, pressure -0.1~1.0MPa.
Preferably, Rosinpolyether copolymer, the SO described in step 2)3Molar ratio be 1：(1~1.7).
Preferably, the Rosinpolyether copolymer described in step 2), solvent mass ratio be 1：(1~5).
Preferably, the solvent described in step 2) for petroleum ether, n-hexane, ethyl acetate, acetone, methanol, ethyl alcohol, chloroform,
At least one of dichloromethane.
Preferably, contain SO described in step 2)3Gaseous mixture in SO3Volume fraction for 1%~6%, the temperature of gaseous mixture
Higher than 50 DEG C, ensure SO3In gaseous state.
Preferably, step 1) and 2) described in aging carried out at 40~90 DEG C, ageing time be 25~70min.
The present invention is made further explanation and description with reference to specific embodiment.
Embodiment 1：
A kind of Rosinpolyether sulfonate, preparation method are as follows：
1) synthesis of Rosinpolyether copolymer：In 500mL stainless steel cauldrons add in acrylic acid rosin (20g,
0.053mol), stirring is warming up to 120 DEG C of meltings, adds in potassium hydroxide (0.9g, 0.02mol), and it is micro to vacuumize 0.5h removings
Water and low-boiling point material, then use N2Residual air in replacement reaction kettle, 155~165 DEG C of controlling reaction temperature, pressure 0.3~
Propylene oxide (123g, 2.1mol, 40eq) is added dropwise in 0.4MPa, continuous-stable, and aging is absorbed into negative pressure, then 0.3~
Under 0.4MPa, ethylene oxide (140g, 3.18mol, 60eq) is added dropwise in continuous-stable, and aging absorbs, and cooling obtains Rosinpolyether and is total to
Polymers (hydroxyl value：10.3mgKOH/g relative molecular weight：About 5340g/mol)；
2) synthesis of Rosinpolyether sulfonate：Rosinpolyether copolymer (50g, 10mmol) is disperseed with chloroform (50g), so
Afterwards and containing SO3Gaseous mixture (SO3：0.9g, 11mmol, N2Dilution, SO3Volume fraction：1%) while from top it is passed through falling film type
In xanthator (shown in Fig. 1), 50 DEG C of reaction temperature further carries out aging, 40 DEG C of aging temperature, and ageing time 25min adds
The NaOH solution for entering mass fraction 10% is neutralized to pH=8, removes solvent chloroform, obtains Rosinpolyether sulfonate.
Embodiment 2：
A kind of Rosinpolyether sulfonate, preparation method are as follows：
1) synthesis of Rosinpolyether copolymer：In 500mL stainless steel cauldrons add in acrylic acid rosin (20g,
0.053mol), stirring is warming up to 120 DEG C of meltings, adds in potassium hydroxide (0.6g, 0.01mol), and it is micro to vacuumize 0.5h removings
Water and low-boiling point material, then use N2Residual air in replacement reaction kettle, 155~165 DEG C of controlling reaction temperature, pressure 0.3~
Propylene oxide (250.1g, 4.2mol, 80eq) is added dropwise in 0.4MPa, continuous-stable, and aging is absorbed into negative pressure, then 0.3~
Under 0.4MPa, ethylene oxide (349.8g, 7.95mol, 150eq) is added dropwise in continuous-stable, and aging absorbs, and cooling obtains rosin and gathers
Ether copolymer (hydroxyl value：12.5mgKOH/g relative molecular weight：About 11696.2g/mol)；
2) synthesis of Rosinpolyether sulfonate：With dichloromethane (150g) by Rosinpolyether copolymer (50g, 4.2mmol)
Dispersion, then and containing SO3Gaseous mixture (SO3：0.5g, 6.3mmol, N2Dilution, SO3Volume fraction：3%) while from top lead to
Enter in falling film sulfonation units (shown in Fig. 1), 65 DEG C of reaction temperature, further carry out aging, 60 DEG C of aging temperature, ageing time
50min, the NaOH solution for adding in mass fraction 10% are neutralized to pH=8, remove methylene chloride, obtain Rosinpolyether sulfonic acid
Salt.
Embodiment 3：
A kind of Rosinpolyether sulfonate, preparation method are as follows：
1) synthesis of Rosinpolyether copolymer：In 500mL stainless steel cauldrons add in acrylic acid rosin (20g,
0.053mol), stirring is warming up to 120 DEG C of meltings, adds in potassium hydroxide (3g, 0.053mol), and it is micro to vacuumize 0.5h removings
Water and low-boiling point material, then use N2Residual air in replacement reaction kettle, 155~165 DEG C of controlling reaction temperature, pressure 0.3~
Propylene oxide (437.8g, 7.42mol, 140eq) is added dropwise in 0.4MPa, continuous-stable, and aging is absorbed into negative pressure, then 0.3~
Under 0.4MPa, ethylene oxide (163.2g, 3.71mol, 70eq) is added dropwise in continuous-stable, and aging absorbs, and cooling obtains Rosinpolyether
Copolymer (hydroxyl value：11mgKOH/g, relative molecular weight：About 11717.7g/mol)；
2) synthesis of Rosinpolyether sulfonate：Rosinpolyether copolymer (50g, 4.2mmol) is divided with petroleum ether (250g)
It dissipates, then and containing SO3Gaseous mixture (SO3：0.6g, 7.3mmol, N2Dilution, SO3Volume fraction：6%) it while from top is passed through
In falling film sulfonation units (shown in Fig. 1), 80 DEG C of reaction temperature further carries out aging, 90 DEG C of aging temperature, ageing time
70min, the NaOH solution for adding in mass fraction 10% are neutralized to pH=8, remove solvent petroleum ether, obtain Rosinpolyether sulfonate.
Test case：
The Rosinpolyether sulfonate prepared to Examples 1 to 3 is tested for the property, and test result is as follows shown in table：
The performance test results of the Rosinpolyether sulfonate of 1 Examples 1 to 3 of table
As shown in Table 1：Polyethers conversion ratio, SO in the present invention3Utilization rate and gross activity object content are higher, and the pine prepared
The surface property of fragrant polyether sulfonate is excellent.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of Rosinpolyether sulfonate, it is characterised in that：General structure is：
Wherein, m is 0~100 integer, and n is 0~100 integer, and is 0 during m with n differences.
2. the preparation method of Rosinpolyether sulfonate described in claim 1, it is characterised in that：Include the following steps：
1) synthesis of Rosinpolyether copolymer：By acrylic acid rosin and catalyst mixing, propylene oxide is added in, is fully reacted, always
Change, add ethylene oxide, fully react, aging obtains Rosinpolyether copolymer；
2) synthesis of Rosinpolyether sulfonate：Rosinpolyether copolymer solvent is disperseed, then be passed through falling film sulfonation from top
Device makes it be flowed down along inner wall, while is passed through from top containing SO3Gaseous mixture, fully react, aging, remove solvent, adjust pH
Value, obtains Rosinpolyether sulfonate.
3. preparation method according to claim 2, it is characterised in that：Catalyst described in step 1) is alkali metal hydroxide
Object, double metal cyanide, bimetallic oxide one kind.
4. preparation method according to claim 2, it is characterised in that：Acrylic acid rosin, catalyst, ring described in step 1)
Ethylene Oxide, ethylene oxide molar ratio be 1：(0.2~1)：(40~150)：(60~180).
5. preparation method according to claim 4, it is characterised in that：Propylene oxide, ethylene oxide described in step 1)
Molar ratio is (0.3~2)：1.
6. the preparation method according to any one in claim 2~5, it is characterised in that：Reaction described in step 1) exists
It is carried out under conditions of 120~180 DEG C of temperature, pressure -0.1~1.0MPa.
7. preparation method according to claim 2, it is characterised in that：Rosinpolyether copolymer, SO described in step 2)3's
Molar ratio is 1：(1~1.7).
8. the preparation method according to claim 2 or 7, it is characterised in that：It is Rosinpolyether copolymer described in step 2), molten
The mass ratio of agent is 1：(1~5).
9. the preparation method according to claim 2 or 7, it is characterised in that：Solvent described in step 2) is petroleum ether, just oneself
At least one of alkane, ethyl acetate, acetone, methanol, ethyl alcohol, chloroform, dichloromethane；Contain SO described in step 2)3Mixing
SO in gas3Volume fraction be 1%~6%.
10. preparation method according to claim 2, it is characterised in that：Step 1) and 2) described in aging at 40~90 DEG C
Lower progress, ageing time are 25~70min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583498A (en) * | 2021-07-28 | 2021-11-02 | 泗县钧科新材料科技有限公司 | Environment-friendly interior wall putty powder and preparation method thereof |
| CN113801440A (en) * | 2021-07-28 | 2021-12-17 | 泗县绿昂新材料科技有限公司 | Packaging winding film and preparation method thereof |
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| CN1039803A (en) * | 1988-07-20 | 1990-02-21 | 国际壳牌研究有限公司 | The method for preparing internal olefin sulphonates |
| CN101321582A (en) * | 2005-12-21 | 2008-12-10 | 剑米索恩公司 | Method and device for the sulfonation or sulfation of sulfonatable or sulfatable organic substances and for preforming faster, strongly exothermic gas7liquid reactions |
| CN101712754A (en) * | 2009-10-16 | 2010-05-26 | 南京擎宇化工研究有限公司 | Gemini-like rosin segmented polyether sulfonate, preparation method and application thereof |
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2017
- 2017-12-14 CN CN201711335006.4A patent/CN108176326A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039803A (en) * | 1988-07-20 | 1990-02-21 | 国际壳牌研究有限公司 | The method for preparing internal olefin sulphonates |
| CN101321582A (en) * | 2005-12-21 | 2008-12-10 | 剑米索恩公司 | Method and device for the sulfonation or sulfation of sulfonatable or sulfatable organic substances and for preforming faster, strongly exothermic gas7liquid reactions |
| CN101712754A (en) * | 2009-10-16 | 2010-05-26 | 南京擎宇化工研究有限公司 | Gemini-like rosin segmented polyether sulfonate, preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583498A (en) * | 2021-07-28 | 2021-11-02 | 泗县钧科新材料科技有限公司 | Environment-friendly interior wall putty powder and preparation method thereof |
| CN113801440A (en) * | 2021-07-28 | 2021-12-17 | 泗县绿昂新材料科技有限公司 | Packaging winding film and preparation method thereof |
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Application publication date: 20180619 |