CN1180076A - Method for preparing end amino or polyamino polymer - Google Patents
Method for preparing end amino or polyamino polymer Download PDFInfo
- Publication number
- CN1180076A CN1180076A CN 97106263 CN97106263A CN1180076A CN 1180076 A CN1180076 A CN 1180076A CN 97106263 CN97106263 CN 97106263 CN 97106263 A CN97106263 A CN 97106263A CN 1180076 A CN1180076 A CN 1180076A
- Authority
- CN
- China
- Prior art keywords
- agent
- aminolysis
- initiator
- formula
- sulfo group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyethers (AREA)
- Paints Or Removers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The preparation method of terminal amino polymer or polyamino polymer is characterized by using hydroxy-terminal polyolefine or hydroxy-terminal polyoxyolfeine as initiator, and firstly using sulfonyl chloride to make sulfonic esterification, then aminolysizing the obtained terminal sulfonated polyester compound by using aminolysizing agent. Said method is mild in reaction condition, its raw materials are easily available, and its product fluidity is good, so that said invention can be extensively used in the fields of coating material, amine adhesive, plastics, petroleum, textile and printing and dyeing industries, etc..
Description
The present invention relates to a kind of macromolecular compound---the synthetic method of end amine based polymer and polyamines based polyalcohol.
End amine based polymer and polyamines based polyalcohol have in fields such as coating, tackiness agent, plastics, oil, weaving and printing and dyeing very to be used widely.At present, the method for preparing end amine based polymer and polyamines based polyalcohol is a lot, United States Patent (USP) (1) USP4202987, (2) 4191835, (3) 379261, (4) 4187367 grades all disclose preparation method separately, and (Guangzhou chemistry) also disclosed a kind of method for preparing polyether polyamine in 1991.Aforesaid method all existed many defectives in implementing kind, the polymericular weight of the described method preparation of document (1) is little, and the fusing point height is difficult for mixing with Resins, epoxy, and the solidification value height of cured epoxy resin; And the disclosed technology of other documents also all exists severe reaction conditions, and environmental pollution is serious, and various defectives such as raw material sources difficulty need a kind of new preparation method of development research to satisfy demand of practical production for this reason.
The objective of the invention is to overcome the shortcoming of prior art, proposing a kind of is the initial action raw material from terminal hydroxy group polyolefine or terminal hydroxy group polyoxygenated alkene directly, at normal temperatures and pressures, by simple reactions steps, prepares the method for end amido or polyamines based polyalcohol.
Design of the present invention is such:
(1) is initiator with terminal hydroxy group polyolefine or terminal hydroxy group polyoxygenated alkene, carries out the sulphur esterification, terminal hydroxy group is sealed, form end sulfo group carboxylate with SULPHURYL CHLORIDE.
(2) above-mentioned carboxylate is used aminolysis agent aminolysis, connected amido, can obtain said end amido or polyamines based polyalcohol at polyolefine or polyoxyalkylene hydrocarbon molecule two ends.
(3) select the molecular weight and the hydroxy functional group number of different terminal hydroxy group polyolefine and terminal hydroxy group polyoxygenated alkene, can obtain to have the amine based polymer of different molecular weight and functional group's number; Select different aminolysis agent,, just can obtain to have the polymkeric substance of corresponding amido at two ends as polyamines, primary monoamine and secondary amine compound.
The present invention also is achieved in that
The structural formula of end amine based polymer of the present invention and polyamines based polyalcohol is respectively shown in formula (1) and the formula (2):
Wherein: R
1Be C
nH
2n, C
nH
nAmong the N-one;
In n=2~6 one;
R
2Be H, CH
3, C
6H
5In one;
R
4, R
3Be H, CH
3, among the OH one;
M is 20~200;
L is 5~200.
The initiator that adopts during polymkeric substance shown in the preparation formula (1) is the terminal hydroxy group polyolefine, and its structural formula is shown in the formula (3), and USP3157604 discloses the preparation method of compound shown in the formula (3),
During polymkeric substance shown in the preparation formula (2), the initiator of employing is the terminal hydroxy group polyoxygenated alkene with different functional groups degree, and its structural formula is shown in the formula (4), J.Chem.Soc., and 1345, (1959) disclose the preparation method of compound shown in the formula (4),
Wherein: R
2, R
5, m, L be all same as above.The contriver has proposed following synthetic method through studying for a long period of time:
1. formula (3) or the described initiator of formula (4) are placed the reactor that stirring, heating and reflux are housed; adding catalyzer, sulfonyl agent carry out the sulphur esterification; temperature of reaction is-5 ℃~40 ℃; best esterification temperature is-5 ℃~20 ℃; react under normal pressure and nitrogen protection, the reaction times is 6~10 hours, and it is extremely neutral with the saturated common salt water washing that products therefrom filters the back; isolate supernatant liquid, can obtain end sulfo group carboxylate.
The reaction expression that initiator shown in the formula (3) carries out the sulphur esterification is:
The reaction expression that initiator shown in the formula (4) carries out the sulphur esterification is:
Wherein: R
2, R
5All same as above.
Described sulphur esterifying agent is Tosyl chloride or Methanesulfonyl chloride; Described sulphur catalyst for esterification is triethylamine or pyridine and composition thereof, and wherein the result of use of triethylamine is even more ideal.The mol ratio of initiator and SULPHURYL CHLORIDE is 1: 5 to 1.2: 1.
2. will hold get final product behind the sulfo group carboxylate aminolysis the compound shown in formula (1) or the formula (2).The reaction expression that is carried out aminolysis by the end sulfo group carboxylate of formula (3) preparation is:
The reaction expression that is carried out aminolysis by the sulfo group carboxylate of formula (4) preparation is:
Wherein: R
1, R
2, R
3, R
4, R
5All same as above.
The aminolysis process is as follows: have in the reactor of stirring, heating and reflux one, add aminolysis agent and precipitation agent, drip above-mentioned end sulfo group carboxylate and carry out aminolysis under normal pressure, the aminolysis temperature is 80~150 ℃, optimum temps is 80~130 ℃, and the reaction times is 6~8 hours.Reaction product is filtered, and it is end amido or the polyamines based polyalcohol shown in formula (1) or the formula (2) that the vacuum removal solvent promptly gets structural formula:
Described aminolysis agent is the compound with following structure:
Wherein: R
1, R
3, R
4All same as above, Y is H, OH, CH
3,
In a kind of, as mphenylenediamine, pinane piperazine, butylamine, Ursol D and Yi Bingchunan etc.; Described precipitation agent is machine solvents such as toluene, hexanaphthene and benzene, and the mol ratio of aminolysis agent and end sulfo group carboxylate is 3: 1 to 1: 1, and precipitation agent and end sulfo group carboxylate volume ratio are 4: 1 to 1: 1.
Adopt method of the present invention, raw material is easy to get, the reaction conditions gentleness, and the molecular weight of products therefrom is 600~6000, good fluidity easily mixes with other high molecular polymer.
Embodiment one
With terminal hydroxy group polyhutadiene (M
n=2000, hydroxyl value 55mgKOH/g) 54g, Tosyl chloride 124g, pyridine 30.3g add in the there-necked flask, holding temperature-5 ℃, stirring and dissolving.Reaction times is 16 hours.After-filtration is finished in reaction, gets light yellow liquid, and washing is got upper strata liquid to neutral in the impouring saturated aqueous common salt.Get another there-necked flask (the stirring and refluxing device is arranged), add mphenylenediamine 30.5g, precipitation agent toluene 90ml, be warmed up to 100 ℃, begin to reflux, be added dropwise to above-mentioned esterifying liquid, react after 10 hours, the cooling, filter light yellow liquid, vacuum is sloughed solvent and mphenylenediamine, promptly gets polyamines base polyhutadiene.
Its total reaction productive rate is 91.2%, and number average functional group degree is 5.4, and viscosity is 3.1PaS.
Embodiment two
Terminal hydroxy group polyhutadiene (Mn=6000, hydroxyl value is 21.3mgKOH/g) 235g replaces the terminal hydroxy group polyhutadiene in the example one, Methanesulfonyl chloride 116g, triethylamine 18.6g, 20 ℃ of holding temperatures, reaction times is 6 hours, and esterification finishes after aminolysis (as described in example 1) is carried out in washing again, wherein the aminolysis agent is pinane piperazine 61g, the aminolysis reaction temperature is 130 ℃, and precipitation agent is a hexanaphthene, must hold the amido polyolefin polymer.
Its total reaction productive rate is 81.9%, and number average functional group number is 1.5.
Embodiment three
Terminal hydroxy group poly styrene polymer (Mn=600, hydroxyl value is 233mgKOH/g) 24.6g replaces the terminal hydroxy group polyhutadiene, and all operating process are as described in the example one.Make the polyamines base polystyrene.
The total reaction productive rate is 86.3%, and functional group's number is 1.6, and viscosity is 0.21PaS.
Embodiment four
With terminal hydroxy group polyoxytrimethylene (Mn=300, hydroxyl value is 244mgKOH/g) 100g, Tosyl chloride 120g, tetrahydrofuran (THF) 60ml drops in the reactor, splashes into triethylamine 40g then, keeps temperature of reaction below 40 ℃, react after 4 hours, to neutral, get the sulphur carboxylate with the saturated common salt water washing.In another reactor, drop into Ursol D 30g, benzene 30ml, temperature of reaction is 80 ℃, reacts after 8 hours, vacuum removal solvent and remaining Ursol D filter and promptly get polyamines base polyoxytrimethylene.
Its total reaction productive rate is 94.7%, and number average functional group number is 5.7, and viscosity is 0.16PaS.
Embodiment five
Hydroxy terminated polyethylene oxide (Mn=2000, hydroxyl value is 55mgKOH/g) 220g replaces the terminal hydroxy group polyoxytrimethylene in the example four, and the aminolysis agent is Yi Bingchunan 45g, and other are operated all with example four.Promptly make end amido polyoxyethylene.
The total reaction productive rate is 92%, and number average functional group number is 1.6, and viscosity is 1.6PaS.
Comparison example
According to the disclosed preparation method of U.S. Pat P4191835, its preparation process is as follows: 46.5g urea and 420g hydroxyl end polyoxytrimethylene amine are joined in the reactor that heating, stirring, backflow and airway are housed, 110 ℃ of holding temperatures, dissolving, reacted 6 hours down at 125~130 ℃, emit 2molNH
3Gas promptly gets thick liquid, this reactant is joined in another reactor that heating, stirring and refluxing and airway are housed, and with the dissolving of 650ml toluene, adds KOH0.5g, and 80 ℃ of holding temperatures add the 68.7g isatoic anhydride, emit CO
2, after 1.5 hours, use NH
3The OH washing, and refining with chloroform extraction, promptly getting and hold amine based polymer, fusing point is 40 ℃.
By above embodiment and Comparative Examples as seen, preparation process of the present invention is simple, and raw material is easy to get, and molecular weight can be between 600~6000, and good fluidity, are a kind of very promising preparation methods.
Obviously, design disclosed according to the present invention and embodiment are about the professional can adopt other terminal hydroxy group polyolefine with different molecular weight and different hydroxyl values or synthetic said end amido of the present invention of terminal hydroxy group polyoxygenated alkene or polyamines based polyalcohol easily.
Claims (7)
1. a new method for preparing end amine based polymer or polyamines based polyalcohol is characterized in that comprising the steps: successively
(1) initiator and catalyzer are placed reactor; under normal pressure and nitrogen protection; carry out the sulphur esterification with sulfonyl agent; reaction times is 6~10 hours; products therefrom is extremely neutral with the saturated common salt water washing; isolate supernatant liquid, obtain a class intermediate product---end sulfo group carboxylate, its reaction expression is respectively shown in formula (a) and the formula (b):
Wherein: R
2Be H, CH
3, C
6H
5, in a kind of; R
5Be H, CH
3In a kind of; M is 20~200; L is 5~200,
Said initiator is terminal hydroxy group polyolefine or terminal hydroxy group polyoxygenated alkene; Said catalyzer is pyridine or triethylamine; Said sulphonating agent is a kind of in toluene sulfonyl chloride or the Methanesulfonyl chloride;
(2) will hold the sulfo group carboxylate to be added drop-wise to and carry out aminolysis reaction in the reactor that aminolysis agent and precipitation agent are housed, react 6~8 hours, product is filtered, the vacuum removal solvent promptly gets said end amine based polymer of the present invention or polyamines based polyalcohol.
Said its general structure of aminolysis agent is:
Wherein: R
1Be C
nH
2n, C
nH
nAmong the N-one; R
3, R
4Be respectively H, CH
3, among the OH one; Y is H, OH, CH
3,
In one; In n=2~6 one; Aminolysis agent commonly used is in mphenylenediamine, pinane piperazine, butylamine, Ursol D, the Yi Bingchunan one;
2. according to the described method of claim 1, it is characterized in that the sulphur esterification temperature is-5~40 ℃.
3. according to the described method of claim 1, it is characterized in that the aminolysis temperature is 80~130 ℃.
4. according to claim 1,2,3 described methods, the mol ratio that it is characterized in that initiator and sulfonyl agent is 5: 1~1: 1.
5. according to claim 1,2,3 described methods, the mol ratio that it is characterized in that initiator and catalyzer is 5: 1~1.2: 1.
6. according to claim 1,2,3 described methods, it is characterized in that holding the mol ratio of sulfo group carboxylate and aminolysis agent is 1: 3~1: 1.
7. according to claim 1,2,3 described methods, it is characterized in that the volume ratio of precipitation agent and end sulfo group carboxylate is 4: 1~2: 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN97106263A CN1073126C (en) | 1997-02-03 | 1997-02-03 | Method for preparing end amino or polyamino polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN97106263A CN1073126C (en) | 1997-02-03 | 1997-02-03 | Method for preparing end amino or polyamino polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1180076A true CN1180076A (en) | 1998-04-29 |
CN1073126C CN1073126C (en) | 2001-10-17 |
Family
ID=5168521
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN97106263A Expired - Fee Related CN1073126C (en) | 1997-02-03 | 1997-02-03 | Method for preparing end amino or polyamino polymer |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1073126C (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101812147B (en) * | 2009-02-19 | 2011-08-03 | 中国石油天然气股份有限公司 | Amino-terminated polypropylene and preparation method thereof |
CN115287907A (en) * | 2022-08-23 | 2022-11-04 | 江苏陆亿纺织科技有限公司 | Wear-resistant anti-yellowing fabric and processing technology thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102504065A (en) * | 2011-11-11 | 2012-06-20 | 中国石油天然气集团公司 | Polyamine inhibitor for drilling fluids and method for preparing polyamine inhibitor |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4007239A (en) * | 1970-08-17 | 1977-02-08 | Bayer Aktiengesellschaft | Aromatic diamines |
US4002598A (en) * | 1975-03-06 | 1977-01-11 | Texaco Development Corporation | Polyether urea epoxy curing agent |
US4202987A (en) * | 1977-12-09 | 1980-05-13 | Ciba-Geigy Corporation | Bis-anthranilates |
-
1997
- 1997-02-03 CN CN97106263A patent/CN1073126C/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101812147B (en) * | 2009-02-19 | 2011-08-03 | 中国石油天然气股份有限公司 | Amino-terminated polypropylene and preparation method thereof |
CN115287907A (en) * | 2022-08-23 | 2022-11-04 | 江苏陆亿纺织科技有限公司 | Wear-resistant anti-yellowing fabric and processing technology thereof |
CN115287907B (en) * | 2022-08-23 | 2024-07-12 | 江苏陆亿纺织科技有限公司 | Wear-resistant anti-yellowing fabric and processing technology thereof |
Also Published As
Publication number | Publication date |
---|---|
CN1073126C (en) | 2001-10-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Eaton et al. | The first catalytic iron-mediated [4+ 1] cyclopentenone assembly: stereoselective synthesis of 2, 5-dialkylidenecyclo-3-pentenones | |
Nelson et al. | Ring-opening polymerization of [2] ferrocenophanes with a hydrocarbon bridge: synthesis of poly (ferrocenylethylenes) | |
NZ214401A (en) | Star/comb-branched polyamides and polyamines | |
CN105367806B (en) | A kind of new polyrotaxane and preparation method thereof | |
Nagasaki et al. | Primary amino-terminal heterobifunctional poly (ethylene oxide). Facile synthesis of poly (ethylene oxide) with a primary amino group at one end and a hydroxyl group at the other end | |
CN101258184A (en) | Star polymer and process for production thereof | |
CN109251260A (en) | Active polymerization system based on phosphine base catalysis synthesizing super high molecular weight polymer | |
CN1642643A (en) | Method for preparing metal cyanide catalyst complexes using partially miscible complexing agents | |
CN1073126C (en) | Method for preparing end amino or polyamino polymer | |
CN114308120A (en) | Phosphorus salt amphiphilic dual-functional organic catalyst and preparation method and application thereof | |
D'Haese et al. | Synthesis and reactions of polytetrahydrofuran with thiolanium end groups | |
US3278484A (en) | Organosilicon compounds, methods of preparation and use | |
CN101367938A (en) | Novel fluorine-containing polyamide sulfonylamine polymer and preparation method thereof | |
CN1068346C (en) | Core functionalised star block copolymers | |
CN1133658C (en) | Alkenyl silane functionalization of alkylstyrene homopolymers and copolymers | |
CN101050276A (en) | Polyethyleneglycol of end group of amino acid, and preparation method | |
JP2003212973A (en) | Accelerator for metathesis catalyst | |
CN1199741A (en) | Preparation of polydicyclopentadiene | |
CN1133687C (en) | Polysilazane with line-ring structure and its preparation method | |
CN109593195A (en) | The method of one kettle way preparation functionalization polypeptide | |
CN112029084B (en) | Simple and controllable method for synthesizing alpha-mercapto-omega-hydroxyl polyether by taking thiocarboxylic acid as initiator | |
CN1126767C (en) | Polymer of TEMPO contg. block polyether-polystyrene and its prepn. method | |
Huguet et al. | Polymerization of oxiranylalkylamines and thiiranylalkylamines derived from achiral and racemic secondary amines | |
Li et al. | A study on the reaction kinetics of dendrimerization by FT-IR spectroscopy: Propagation of PAMAM dendrimer on silica gel | |
CN1176120C (en) | Technology of preparing comb shaped polymer by combining atomic transfer free radical and ring opening disproportionation polymerization |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |