CN1962600B - Fatty alcohol polyether dibasic acid ester and its synthesis and uses - Google Patents
Fatty alcohol polyether dibasic acid ester and its synthesis and uses Download PDFInfo
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- CN1962600B CN1962600B CN2006101283268A CN200610128326A CN1962600B CN 1962600 B CN1962600 B CN 1962600B CN 2006101283268 A CN2006101283268 A CN 2006101283268A CN 200610128326 A CN200610128326 A CN 200610128326A CN 1962600 B CN1962600 B CN 1962600B
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- acid ester
- alcohol polyether
- dibasic acid
- fatty alcohol
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Abstract
The invention discloses an aliphatic alcohol polyether dibasic acid ester and synthesizing method and application with the structural formula as R1O (CH2CH2O) m (CH2 (CH3) CHO) nOOCR2COO (CH2CH2O) m (CH2 (CH3) CHO) nR1, wherein R1 is C4-C24 alkyl; R2 is C2-C4 alkylidene; m is 1-30; n is 0-20. The invention can be spinning oil agent, which possesses superior smooth, extending and heat resistance property.
Description
Technical field
The invention belongs to no ring filling multi-carboxylate, particularly a kind of fatty alcohol polyether dibasic acid ester and synthetic and application thereof.
Background technology
The high speed development of domestic synthon brings the growth of finish consumption, cause that finish Development and Production both domestic and external manufacturer is around domestic preparation medium market access work, especially the smooth agent in the preparation medium is developed as the emphasis of finish exploitation, because of the main component in the finish is a smooth agent, and very big to spinning properties and quality product influence, industrial silk oil agent is all the more so.
Smooth agent in the spinning oil mainly contains: 1. mineral oil, 2. vegetable and animals oils, 3. polyoxyethylene carboxylate, 4. fatty acid ester fatty alcohol, 5. polyoxyethylene fatty amine, 6. polyol esters of fatty acids, 7. polyoxyethylene fatty acid polyol ester, 8. Fatty Alcohol(C12-C14 and C12-C18) diester, 9. fatty alcohol-polyoxyethylene ether, 10. polyethers of all size and model etc.The poor heat resistance, the amount of being fuming that have in these smooth agents are big, as mineral oil, fatty alcohol-polyoxyethylene ether; The coking behavior that has is poor, as vegetables oil, unsaturated fatty acid ester fatty alcohol; Being fuming of having is little, and coking is few, and smoothness is excellent, as saturated fatty acid polyol ester, saturated fatty alcohol diester, extraordinary polyethers etc.Using more is polyethers and polyunsaturated fatty acid ester, does not then appear in the newspapers for being applied in the spinning oil by oxyethane and propylene oxide random copolymerization ether and diprotic acid institute synthetic ester.It has high-tenacity, high-modulus, height is sticking and the elongation at break of property and appropriateness, continuous rating elongation rate etc. and the purposes of industry silk requires, satisfy can being realized of these requirements by improvement such as spinning technique, raw material and variation, and also can reach this purpose to a certain extent by exploitation to the main component smooth agent in the finish, smooth agent commonly used needs two or more can satisfy this requirement, and fatty alcohol polyether dibasic acid ester of the present invention is a kind of can to satisfy multiple performance demands and only need use in the finish.
The patent documentation identical with fatty alcohol polyether dibasic acid ester do not have report, and close patent is as follows:
USP3959187 discloses a kind of alkyl alcohol Soxylat A 25-7 polybasic ester that is applied in the spinning oil, this ester can be applicable in spinning oil and the metal processing oil solution, in spinning oil, have good thermotolerance, smoothness and emulsifying property, but when using as high performance industrial silk oil agent monomer, its drawing-off poor performance shows as its continuous rating elongation rate of industry silk that spun and elongation at break height and brute force is lower.Patent of the present invention is by changing molecular structure, promptly adopt alkyl alcohol (Fatty Alcohol(C12-C14 and C12-C18)) polyoxyethylene poly-oxygen propylene aether diester, in molecule, increased the polyoxypropylene modular construction, thereby further improved the thermotolerance of finish, especially improved the drawing-off performance of finish, be suitable as the industry silk principal monomer of high-speed spun PA tyre cord oiling agent especially with high drawdown, institute's spinning tyre cord precursor has high brute force and moderate continuous rating elongation rate and elongation at break.
USP5972497 has introduced a kind of pentaerythritol ester as the spinning oil smooth agent, the smoothness and the softness of pentaerythritol ester are good, add static inhibitor and other monomer, be well suited for main component as short-fiber oil agent, excellent propertys such as its flexibility, crimp tendency, crush cutting, cardability, blending, but as if the smooth agent as industrial silk oil agent, then drawdown, holding etc. are difficult to meet the demands, promptly spin the powerful low of industry silk, and continuous rating elongation rate and elongation at break height.Patent of the present invention is by increasing polyether structure in the diester molecule, especially by changing the ratio of oxyethane and propylene oxide in the pfpe molecule, to improve drawdown, holding and the smoothness etc. of fatty alcohol polyether dibasic acid ester, make the powerful high of the industry silk that spins, and continuous rating elongation rate and elongation at break are moderate.
CN1284512A discloses the synthetic method of a kind of alkyl, polyether fatty acid ester (polyether ester), its alkyl is butyl, octyl group, lauryl etc., lipid acid is monoprotic acid, as lauric acid, palmitinic acid, oleic acid, stearic acid etc., this polyethers is applied in has good smoothness, holding, thermotolerance and emulsifying property in the spinning oil, be applicable to civilian silk oil agent or the agent of general industry silk oil, but its drawing-off poor performance is not suitable for use in high ratio of drawing, high performance industrial silk spinning silk oil agent monomer use.And what described polyether fatty acid ester was used is that polyethers and monobasic acid ester synthesize, and the present invention is by using polyethers and diester synthetic, keeping good smoothness, holding, thermotolerance and the emulsifying property while that polyether ester had, possesses good drawing-off performance again, if the industry silk uses as cord fabrics, polyether dibasic acid ester then of the present invention also can improve the sticking and performance of cord fabrics and rubber.
The synthetic ester that above patent is introduced is also applicable to agent of civilian silk spinning silk oil or the less demanding industrial silk oil agent of counter extensioin.
Relevant polyethers patent synthetic and that use is a lot, but the overwhelming majority is to be applied to aspects such as emulsion splitter, urethane plastic, wetting agent, washing composition, defoamer, dispersion agent and other additive, as USP6316586, USP6458918, the polyethers that USP6683222 etc. introduced is not suitable for being applied in the spinning oil, and the smoothness of polyethers under high temperature, high speed and high ratio of drawing condition that can be applicable in the spinning oil is relatively poor.Be applied in the spinning oil and special polyethers (certain molecular weight, molecular structure, initiator, oxyethane and propylene oxide ratio etc.) and diprotic acid are carried out the resulting synthetic ester of esterification, but have good thermotolerance, smoothness and drawdown.
Summary of the invention
The object of the present invention is to provide a kind of fatty alcohol polyether dibasic acid ester, this fatty alcohol polyether dibasic acid ester has good smoothness, drawdown and thermotolerance, be applicable to polyamide fibre industry silk, the polyester industrial yarn finish of high-performance, high ratio of drawing, make finish use the least possible monomer kind and can reach good use properties.
The structural formula of fatty alcohol polyether dibasic acid ester of the present invention is:
R
1O(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nOOCR
2COO(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nR
1
R wherein
1Be C
4～C
24Alkyl, C preferably
4～C
18Alkyl; R
2Be C
2～C
24Alkylidene group, promptly lack a H atom than corresponding alkyl; M is 1～30, best 4～26; N is 0～20, is preferably 2～14.
The synthetic method of fatty alcohol polyether dibasic acid ester of the present invention is as follows:
1) aliphatic alcohol polyether is synthetic: with the carbon number is C
4～C
24, best C
4～C
18N-alkanol be initiator, the adding mass ratio is 100/0～10/90 oxyethane (EO) and propylene oxide (PO), and then adding accounts for reactant gross weight 0.02～1 weight %, be preferably the iron that contains of 0.05～0.2 weight %, the bimetallic catalyst of cobalt, or account for reactant gross weight 0.1～0.8 weight %, be preferably the sodium hydroxide catalyst of 0.2～0.5 weight %, 100～160 ℃ of temperature of reaction, best 110～130 ℃, reaction pressure 0.2～0.6MPa, best 0.3～0.4Mpa, 60～90 minutes reaction times, carrying out polymerization, to obtain molecular weight be 500～2000, is preferably 800～1500 aliphatic alcohol polyether.
2) fatty alcohol polyether dibasic acid ester is synthetic:
Step 1) synthetic aliphatic alcohol polyether and C
2～C
24Diprotic acid carry out esterification and obtain fatty alcohol polyether dibasic acid ester, the structural formula of fatty alcohol polyether dibasic acid ester is:
R
1O(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nOOCR
2COO(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nR
1
Wherein step 1) synthetic aliphatic alcohol polyether and C
2～C
24The mol ratio of diprotic acid be 2.0～2.6: 1, be preferably 2.2～2.4: 1, temperature of reaction is 160～240 ℃, be preferably 180～220 ℃, the reaction times is 2～8 hours, is preferably 4～6 hours, with tosic acid or tetrabutyl titanate is catalyzer, add-on is 0.05～1.2 weight %, and best 0.2～0.8 weight % is in the reactant gross weight.
The application of fatty alcohol polyether dibasic acid ester of the present invention is with its principal monomer as spinning oil, and its ratio in spinning oil is 10～80 weight %, in the spinning oil gross weight.
Fatty alcohol polyether dibasic acid ester of the present invention is as the spinning oil monomer, have good thermotolerance, smoothness, convergency and emulsifying property, especially as high performance industrial silk oil agent monomer, the drawing-off excellent property, show as and use the finish that contains fatty alcohol polyether dibasic acid ester, the powerful height of the industry silk that spins, continuous rating elongation rate and elongation at break are moderate, if the industry silk uses as cord fabrics, then use the sticking and performance that fatty alcohol polyether dibasic acid ester can effectively improve cord fabrics and rubber in the finish.
Embodiment
Describe the present invention in detail with specific examples below, and embodiment does not limit the scope of the invention.
Embodiment 1
Synthesizing of n-hexyl alcohol polyethers adipic acid ester.
The structural formula of n-hexyl alcohol polyethers adipic acid ester is:
C
6H
13O(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nOOCC
4H
8COO(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nC
6H
13
(m=9.2 wherein, n=8.6)
In the exsiccant stainless steel autoclave, add initiator n-hexyl alcohol 51.0 grams, bimetallic catalyst 0.5 gram, install autoclave after, with air in the nitrogen replacement still for several times, and the blow device pipeline.Heat slowly, treat that temperature in the kettle rises to about 70 ℃, vacuumize and slough moisture in the initiator, in still, charge into nitrogen then to pressure-fired, slowly add oxyethane and propylene oxide mixture 449.0 grams after measuring continuously, EO/PO=45/55 (mass ratio wherein, down together), control pressure is at 0.2～0.3MPa, temperature is 120～130 ℃, after charging finishes, continue reaction 1 hour, then cooling, with the entrap bubble in nitrogen purge line and the reactor, the gained polyethers can carry out the synthetic of next step after making with extra care and filter with activated carbon.
Get above-mentioned gained polyethers 220.0 grams; hexanodioic acid 14.6 gram (polyethers and hexanodioic acid by 2.2: 1 mol ratio) joins in three mouthfuls of glass flask; add 0.5% catalyzer tosic acid then; under 200～220 ℃ of temperature; nitrogen protection; stirring reaction 4 hours, cooling can obtain the described faint yellow polyether dibasic acid ester of this patent then.
Embodiment 2
Synthesizing of propyl carbinol polyethers succinate.
The structural formula of propyl carbinol polyethers succinate is:
C
4H
9O(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nOOCC
2H
4COO(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nC
4H
9
(m=16 wherein, n=12).
In the exsiccant stainless steel autoclave, add initiator propyl carbinol 24.7 grams, sodium hydroxide catalyst 1.0 grams, install autoclave after, with air in the nitrogen replacement still for several times, and the blow device pipeline.Heat slowly, treat that temperature in the kettle rises to about 70 ℃, vacuumize and slough moisture in the initiator, in still, charge into nitrogen then to pressure-fired, slowly add oxyethane and propylene oxide mixture 475.3 grams after measuring continuously, EO/PO=50/50 wherein, control pressure is at 0.3～0.4MPa, temperature is 110～120 ℃, after charging finishes, continue reaction 1 hour, cooling then, with the entrap bubble in nitrogen purge line and the reactor, the gained polyethers can carry out the synthetic of next step after making with extra care and filter with activated carbon.
Get above-mentioned gained polyethers 360.0 grams; Succinic Acid 11.8 gram (polyethers and Succinic Acid by 2.4: 1 mol ratio) joins in three mouthfuls of glass flask; add 0.3% catalyzer metatitanic acid four butyl esters then; under 180～200 ℃ of temperature; nitrogen protection; stirring reaction 6 hours, cooling can obtain the described faint yellow polyether dibasic acid ester of this patent then.。
Embodiment 3
Synthesizing of laureth sebate.
The structural formula of laureth sebate is:
C
12H
25O(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nOOCC
2H
4COO(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nC
12H
25
(m=7.7 wherein, n=4.8)
In the exsiccant stainless steel autoclave, add initiator lauryl alcohol 93.0 grams, bimetallic catalyst 0.25 gram, install autoclave after, with air in the nitrogen replacement still for several times, and the blow device pipeline.Heat slowly, treat that temperature in the kettle rises to about 70 ℃, vacuumize and slough moisture in the initiator, in still, charge into nitrogen then to pressure-fired, slowly add oxyethane and propylene oxide mixture 307.0 grams after measuring continuously, EO/PO=55/45 wherein, control pressure is at 0.3～0.4MPa, temperature is 110～120 ℃, after charging finishes, continue reaction 1.5 hours, cooling then, with the entrap bubble in nitrogen purge line and the reactor, the gained polyethers can carry out the synthetic of next step after making with extra care and filter with activated carbon.
Get above-mentioned gained polyethers 300.0 grams; sebacic acid 37.9 gram (polyethers and sebacic acid by 2.0: 1 mol ratio) joins in three mouthfuls of glass flask; add 0.3% catalyzer tosic acid then; under 220～240 ℃ of temperature; nitrogen protection; stirring reaction 5 hours, cooling can obtain the described faint yellow polyether dibasic acid ester of this patent then.。
Embodiment 4
Synthesizing of n-Octanol polyethers azelate.
The structural formula of n-Octanol polyethers azelate is:
C
8H
17O(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nOOCC
7H
14COO(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nC
8H
17
(m=12.2 wherein, n=9.2)
In the exsiccant stainless steel autoclave, add initiator n-Octanol 52.0 grams, bimetallic catalyst 0.3 gram, install autoclave after, with air in the nitrogen replacement still for several times, and the blow device pipeline.Heat slowly, treat that temperature in the kettle rises to about 70 ℃, vacuumize and slough moisture in the initiator, in still, charge into nitrogen then to pressure-fired, slowly add oxyethane and propylene oxide mixture 428.0 grams after measuring continuously, EO/PO=50/50 wherein, control pressure is at 0.3～0.4MPa, temperature is 115～125 ℃, after charging finishes, continue reaction 1 hour, cooling then, with the entrap bubble in nitrogen purge line and the reactor, the gained polyethers can carry out the synthetic of next step after making with extra care and filter with activated carbon.
Get above-mentioned gained polyethers 390.0 grams; nonane diacid 24.4 gram (polyethers and nonane diacid by 2.5: 1 mol ratio) joins in three mouthfuls of glass flask; add 1.0% tosic acid then; under 180～200 ℃ of temperature; nitrogen protection; stirring reaction 4 hours, cooling can obtain the described faint yellow polyether dibasic acid ester of this patent then.
Embodiment 5
The application of n-Octanol polyethers azelate.
The structural formula of n-Octanol polyethers azelate is:
C
8H
17O(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nOOCC
7H
14COO(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nC
8H
17
(m=12.2 wherein, n=9.2)
Getting embodiment 4 gained n-Octanol polyethers azelates 240.0 grams joins in the 1000ml synthesis reactor, add 325.0 gram aliphatic alcohol polyoxyethylene tensio-active agents then, 25.0 gram static inhibitor and 10.0 restrains other additives such as sticking and improvement in performance agent, 40～45 ℃ were stirred 40 minutes down, can obtain high-speed spun PA-6 tyre cord oiling agent, this finish possesses good drawdown and sticking and property again when possessing good heat resistance, smoothness.
Embodiment 6
Synthetic and the application of positive stearyl alcohol polyethers succinate.
The structural formula of positive stearyl alcohol polyethers succinate is:
C
18H
37O(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nOOCC
2H
4COO(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nC
18H
37
(m=15.4 wherein, n=7.8)
In the exsiccant stainless steel autoclave, add initiator stearyl alcohol 81.0 grams, sodium hydroxide catalyst 1.0 grams, install autoclave after, with air in the nitrogen replacement still for several times, and the blow device pipeline.Heat slowly, treat that temperature in the kettle rises to about 70 ℃, vacuumize and slough moisture in the initiator, in still, charge into nitrogen then to pressure-fired, slowly add oxyethane and propylene oxide mixture 339.0 grams after measuring continuously, EO/PO=60/40 wherein, control pressure is at 0.3～0.4MPa, temperature is 110～120 ℃, after charging finishes, continue reaction 1.5 hours, cooling then, with the entrap bubble in nitrogen purge line and the reactor, the gained polyethers can carry out the synthetic of next step after making with extra care and filter with activated carbon.
Get above-mentioned gained polyethers 294.0 grams; Succinic Acid 11.8 gram (polyethers and Succinic Acid by 2.1: 1 mol ratio) joins in three mouthfuls of glass flask; add 0.3% catalyzer metatitanic acid four butyl esters then; under 210～230 ℃ of temperature, nitrogen protection, stirring reaction 6 hours; cooling can obtain the described faint yellow polyether dibasic acid ester of this patent then.
Embodiment 7
Get other additives such as embodiment 5 gained n-Octanol polyethers azelates, aliphatic alcohol polyoxyethylene tensio-active agent, static inhibitor, sticking and improvement in performance agent, 40～45 ℃ were stirred 40 minutes down, can obtain high-speed spun PA-6 tyre cord oiling agent, this finish as be high-speed spun PA-6 tyre cord oiling agent in industrial test, the results are shown in Table 1.
Table 1 polyether dibasic acid ester is as the monomeric commercial test results of finish
| Content in the finish, % | Finish is fuming and the tar voltinism | The finish spinning property | The precursor brute force of spinning, N * | The precursor that spins is stretched surely, % * | Institute's precursor that spins is disconnected stretches % * | With cord fabrics adhesion, N ** |
| 20 | The little tar of cigarette is few | Well | 156.5 | 11.5 | 22.8 | 186.2 |
| 35 | The little tar of cigarette is few | Well | 157.2 | 11.4 | 22.0 | 192.4 |
| 50 | The little tar of cigarette is few | Well | 158.0 | 11.2 | 21.2 | 194.0 |
*Nylon-6 industry silk, specification is 1870dtex
*The cord fabrics specification is 1870dtex/2
Table 1 data show, by using the fatty alcohol polyether dibasic acid ester of being invented, i.e. a kind of n-Octanol polyethers azelate (EO/PO=40/60 of pfpe molecule wherein, molecular weight is 800), the thermotolerance of nylon-6 industrial silk oil agent, smoothness, convergency, drawdown and sticking and functional show as that being fuming of finish is little, tar is few, good spinnability, powerful and adhesion height, stretch surely with disconnected stretch moderate.
Embodiment 8
Synthesizing of propyl carbinol polyethers succinate.
The structural formula of propyl carbinol polyethers succinate is:
C
4H
9O(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nOOCC
2H
4COO(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nC
4H
9
(m=3 wherein, n=10)
In the exsiccant stainless steel autoclave, add initiator propyl carbinol 29.6 grams, sodium hydroxide catalyst 0.5 gram, install autoclave after, with air in the nitrogen replacement still for several times, and the blow device pipeline.Heat slowly, treat that temperature in the kettle rises to about 70 ℃, vacuumize and slough moisture in the initiator, in still, charge into nitrogen then to pressure-fired, slowly add oxyethane and propylene oxide mixture 285 grams after measuring continuously, EO/PO=18/82 wherein, control pressure is at 0.3～0.4MPa, temperature is 110～120 ℃, after charging finishes, continue reaction 1 hour, cooling then, with the entrap bubble in nitrogen purge line and the reactor, the gained polyethers can carry out the synthetic of next step after making with extra care and filter with activated carbon.
Get above-mentioned gained polyethers 315.0 grams; Succinic Acid 18.9 gram (polyethers and Succinic Acid by 2.5: 1 mol ratio) joins in three mouthfuls of glass flask; add 0.3% catalyzer tosic acid then; under 180～200 ℃ of temperature; nitrogen protection; stirring reaction 6 hours, cooling can obtain the described polyether dibasic acid ester of this patent then.
Embodiment 9
Synthesizing of propyl carbinol polyethers adipic acid ester.
The structural formula of propyl carbinol polyethers adipic acid ester is:
C
4H
9O(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nOOCC
4H
8COO(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nC
4H
9
(m=11 wherein, n=0)
In the exsiccant stainless steel autoclave, add initiator propyl carbinol 37.0 grams, bimetallic catalyst 0.25 gram, install autoclave after, with air in the nitrogen replacement still for several times, and the blow device pipeline.Heat slowly, treat that temperature in the kettle rises to about 70 ℃, vacuumize and slough moisture in the initiator, charge into nitrogen then to pressure-fired in still, slowly add oxyethane 242.0 grams after measuring continuously, control pressure is at 0.3～0.4MPa, temperature is 110～120 ℃, after charging finishes, continue reaction 1.5 hours, then cooling, with the entrap bubble in nitrogen purge line and the reactor, the gained polyethers can carry out the synthetic of next step after making with extra care and filter with activated carbon.
Get above-mentioned gained polyethers 250.0 grams; hexanodioic acid 26.4 gram (polyethers and hexanodioic acid by 2.0: 1 mol ratio) joins in three mouthfuls of glass flask; add 0.3% catalyzer tosic acid then; under 220～240 ℃ of temperature; nitrogen protection; stirring reaction 5 hours, cooling can obtain the described polyether dibasic acid ester of this patent then.
Embodiment 10
Synthesizing of propyl carbinol polyethers azelate.
The structural formula of propyl carbinol polyethers azelate is:
C
12H
25O(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nOOCC
7H
14COO(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nC
12H
25
(m=11.3 wherein, n=20.0)
In the exsiccant stainless steel autoclave, add initiator propyl carbinol 22.2 grams, bimetallic catalyst 0.25 gram, install autoclave after, with air in the nitrogen replacement still for several times, and the blow device pipeline.Heat slowly, treat that temperature in the kettle rises to about 70 ℃, vacuumize and slough moisture in the initiator, in still, charge into nitrogen then to pressure-fired, slowly add oxyethane and propylene oxide mixture 497.2 grams after measuring continuously, EO/PO=30/70 wherein, control pressure is at 0.3～0.4MPa, temperature is 110～120 ℃, after charging finishes, continue reaction 1.5 hours, cooling then, with the entrap bubble in nitrogen purge line and the reactor, the gained polyethers can carry out the synthetic of next step after making with extra care and filter with activated carbon.
Get above-mentioned gained polyethers 300.0 grams; nonane diacid 16.3 gram (polyethers and nonane diacid by 2.0: 1 mol ratio) joins in three mouthfuls of glass flask; add 0.3% catalyzer tosic acid then; under 220～240 ℃ of temperature; nitrogen protection; stirring reaction 5 hours, cooling can obtain the described polyether dibasic acid ester of this patent then.
Embodiment 11
Synthesizing of laureth adipic acid ester.
The structural formula of laureth adipic acid ester is:
C
12H
25O(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nOOCC
4H
8COO(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nC
12H
25
(m=25.0 wherein, n=8.1)
In the exsiccant stainless steel autoclave, add initiator lauryl alcohol 55.8 grams, bimetallic catalyst 0.25 gram, install autoclave after, with air in the nitrogen replacement still for several times, and the blow device pipeline.Heat slowly, treat that temperature in the kettle rises to about 70 ℃, vacuumize and slough moisture in the initiator, in still, charge into nitrogen then to pressure-fired, slowly add oxyethane and propylene oxide mixture 470.9 grams after measuring continuously, EO/PO=70/30 wherein, control pressure is at 0.3～0.4MPa, temperature is 110～120 ℃, after charging finishes, continue reaction 1.5 hours, cooling then, with the entrap bubble in nitrogen purge line and the reactor, the gained polyethers can carry out the synthetic of next step after making with extra care and filter with activated carbon.
Get above-mentioned gained polyethers 300.0 grams; hexanodioic acid 10.1 gram (polyethers and hexanodioic acid by 2.0: 1 mol ratio) joins in three mouthfuls of glass flask; add 0.3% catalyzer tosic acid then; under 220～240 ℃ of temperature; nitrogen protection; stirring reaction 5 hours, cooling can obtain the described faint yellow polyether dibasic acid ester of this patent then.
Claims (6)
1. fatty alcohol polyether dibasic acid ester is characterized in that structural formula is:
R
1O(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nOOCR
2COO(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nR
1
R wherein
1Be C
4～C
24Alkyl, R
2Be C
2～C
24Alkylidene group, m is 1～30, n is 0～20.
2. according to the described fatty alcohol polyether dibasic acid ester of claim 1, it is characterized in that: m is 4～26, and n is 2～14.
3. according to the described fatty alcohol polyether dibasic acid ester of claim 1, it is characterized in that: R
1Be C
4～C
18Alkyl.
4. the synthetic method of the described fatty alcohol polyether dibasic acid ester of claim 1 is characterized in that comprising the steps:
1) aliphatic alcohol polyether is synthetic: with C
4～C
24N-alkanol be initiator, the adding mass ratio is 100/0～10/90 oxyethane and propylene oxide, and then add the sodium hydroxide catalyst account for the bimetallic catalyst that contains iron, cobalt of reactant gross weight 0.02～1 weight % or to account for reactant gross weight 0.1～0.8 weight %, 100～160 ℃ of temperature of reaction, under the condition of reaction pressure 0.2～0.6Mpa, in 60～90 minutes reaction times, obtain molecular weight and be 500～2000 aliphatic alcohol polyether;
2) polyether dibasic acid ester is synthetic: step 1) synthetic aliphatic alcohol polyether and C
2～C
24Diprotic acid carry out esterification and obtain fatty alcohol polyether dibasic acid ester, the structural formula of fatty alcohol polyether dibasic acid ester is:
R
1O(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nOOCR
2COO(CH
2CH
2O)
m(CH
2(CH
3)CHO)
nR
1
Wherein step 1) synthetic aliphatic alcohol polyether and C
2～C
24The mol ratio of diprotic acid be 2.0～2.6: 1, temperature of reaction is 160～240 ℃, the reaction times is 2～8 hours, is catalyzer with tosic acid or tetrabutyl titanate, the catalyzer add-on is 0.05～1.2 weight %, in the reactant gross weight.
5. according to the described synthetic method of claim 4, be characterised in that: step 1) aliphatic alcohol polyether synthetic temperature of reaction is 110～130 ℃, and reaction pressure is 0.3～0.4MPa; Step 2) aliphatic alcohol polyether and C
2～C
24The diprotic acid mol ratio of carrying out esterification be 2.2～2.4: 1, temperature of reaction is 180～220 ℃, the reaction times is 4～6 hours.
6. the application of the described fatty alcohol polyether dibasic acid ester of claim 1 is characterized in that: the fatty alcohol polyether dibasic acid ester of 10～80 weight % is used for spinning oil as monomer, in the spinning oil gross weight.
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| CN109112586B (en) * | 2018-10-22 | 2020-12-11 | 江苏赛夫特半导体材料检测技术有限公司 | Novel efficient semiconductor copper plating additive and preparation method thereof |
| CN114775325A (en) * | 2022-04-01 | 2022-07-22 | 中国石油化工股份有限公司 | Dispersing agent for aramid fiber paper and preparation method and application thereof |
| CN117143328B (en) * | 2023-08-18 | 2024-04-26 | 山东滨化聚禾新材料科技有限公司 | Preparation method of high-carbon alcohol polyether ester for defoamer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3959187A (en) * | 1973-12-28 | 1976-05-25 | Emery Industries, Inc. | Mixed synthetic ester lubricants as useful polymeric fiber lubricants |
| US5972497A (en) * | 1996-10-09 | 1999-10-26 | Fiberco, Inc. | Ester lubricants as hydrophobic fiber finishes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3959187A (en) * | 1973-12-28 | 1976-05-25 | Emery Industries, Inc. | Mixed synthetic ester lubricants as useful polymeric fiber lubricants |
| US5972497A (en) * | 1996-10-09 | 1999-10-26 | Fiberco, Inc. | Ester lubricants as hydrophobic fiber finishes |
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