CN109265661A - A kind of preparation method of novel polycaprolactone polyol - Google Patents
A kind of preparation method of novel polycaprolactone polyol Download PDFInfo
- Publication number
- CN109265661A CN109265661A CN201811112094.6A CN201811112094A CN109265661A CN 109265661 A CN109265661 A CN 109265661A CN 201811112094 A CN201811112094 A CN 201811112094A CN 109265661 A CN109265661 A CN 109265661A
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- Prior art keywords
- polycaprolactone polyol
- catalyst
- molecular weight
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention discloses a kind of catalyst for preparing polycaprolactone polyol, it is using caprolactone monomer and initiator alcohol as raw material, it is reacted under the effect of the catalyst, obtains polycaprolactone polyol, one of octoate catalyst stannous, new certain herbaceous plants with big flowers acid zinc, 2 ethyl hexanoic acid zinc and zinc oxide are used alone, initiator alcohol refers to 2,2,4,4- tetramethyls -1,3- cyclobutanediol, dosage are adjusted according to the size of required product molecular weight.
Description
Technical field
The present invention relates to the methods for producing novel polycaprolactone polyol, and in particular to preparation is with novel polyalcohol
For initiator, novel polycaprolactone polyol is prepared, polycaprolactone polyol is the primary raw material for preparing polyurethane, is belonged to
Polymeric material field.
Background technique
There is good mechanics and elastic property using the polyurethane that polycaprolactone polyol is prepared as raw material, use extensively
In preparing elastomer, rigid and flexible foams, adhesive and coating etc., in artificial leather, furniture, shoemaking, building, automobile and other industries
It is widely used.The preparation method of polylactone is substantially used using caprolactone as primary raw material at present, using alcohols as initiator, is being urged
Caprolactone ring-opening polymerisation preparation is carried out under the action of agent, alcohols initiator difference obtains the product of different model.About lactone
Ring-opening polymerisation preparation high molecular weight poly-epsilon-caprolactone and the existing a large amount of research of polylactic acid, various catalyst, which become, to be ground
The hot spot studied carefully.Such as CN1814644, US5235031, US5357034, US4057537 are reported with metallic catalysts such as pink salts
It carries out catalysis 6-caprolactone and lactide carries out ring-opening polymerisation and prepares poly-epsilon-caprolactone and polylactic acid.
At present it has been reported that or formed commodity polycaprolactone polyol, initiator alcohol used is usually neopentyl glycol
(NEO), diethylene glycol (DEG), 1,4-butanediol (BDO), 1,6- hexylene glycol (HDO), trimethylolpropane (TMP), Ji Wusi
One of alcohol (PENTA), ethylene glycol (MEG) etc. are led with the polyurethane material application that polycaprolactone polyol is raw material
Domain is widened, and needs some polycaprolactone polyols with higher intensity and new capability, the polyurethane of preparation, which is just able to satisfy, to be wanted
It asks.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of novel polycaprolactone polyol.It is 6-caprolactone (CL) for singly
Body carries out polymerization reaction using novel polyols as initiator under the effect of the catalyst, obtains polycaprolactone polyol, produces
Product molecular weight is usually 300-10000.
The object of the present invention is achieved like this:
The preparation method of this novel polycaprolactone polyol is with 6-caprolactone (CL) for monomer, with 2,2,4,4- tetramethyls-
1,3-cyclobutanediol carries out polymerization reaction under the effect of the catalyst, obtains polycaprolactone polyol as initiator.Polymerization
Condition is similar with the lactone polymerisation condition of report, (inert gas shielding or vacuum generally under the conditions of 60-180 degree, anhydrous and oxygen-free
Under) ring-opening polymerisation is carried out, polymerization time is 1-24 hours, passes through the different available variety classes of the quantity and kind of polyalcohol
And the polycaprolactone polyol of different molecular weight, bulk polymerization can be carried out, solvent can also be added and carry out polymerisation in solution, carry out
Solvent is chloroform, tetrahydrofuran or toluene when polymerisation in solution.Consersion unit is the commonly used equipment of high molecular polymerization, can be interval
Be also possible to continuous device, reach needs the degree of polymerization require after purify with conventional method and removes unreacted monomer and impurity,
Obtain polycaprolactone polyol.
Initiator alcohol of the present invention refers to 2,2,4,4-Tetramethyl-1,3-cyclobutanediol, and dosage is according to required production
The size of product molecular weight is adjusted, and the chemical structural formula of initiator alcohol and novel polycaprolactone polyol is as follows.
2,2,4,4--1,3-cyclobutanediol of tetramethyl
Gather oneself
Lactone polyols
Catalyst used in the present invention is that one of stannous octoate, zinc neodecanoate, 2 ethyl hexanoic acid zinc and zinc oxide individually make
With dosage 0.005-10%.
Outer unless otherwise indicated, molecular weight involved in the present invention is to pass through nuclear magnetic resonance measuring and calculate, molecule
Amount distribution is measured with gel permeation chromatography (GPC), and product hydroxyl value passes through titration measuring.
The embodiment of the present invention is given below, the present invention is specifically described by embodiment.It is necessary to it is pointed out here that
, embodiment is served only for that the present invention is further detailed, and should not be understood as limiting the scope of the invention, should
The person skilled in the art in field can make some nonessential modifications and adaptations according to the content of aforementioned present invention.
Specific embodiment:
Embodiment 1
In 1 liter of vial, 300 grams of CL, 21.6 grams of 2,2,4,4-Tetramethyl-1,3-cyclobutanediol, with nitrogen displacement three are added
After secondary, 0.3 gram of stannous octoate is added under nitrogen protection, is heated to 130-160 degree and reacts 12 hours, unreacted original is removed in vacuum
It is cooled to room temperature after material and obtains 320 grams of polycaprolactone polyol, passing through nuclear magnetic resonance measuring and calculating molecular weight is 2000, warp
GPC measures molecular weight distribution 1.16, hydroxyl value 56mg KOH/g.
Embodiment 2
In 1 liter of vial, 300 grams of CL are added, 14.88 grams of 2,2,4,4-Tetramethyl-1,3-cyclobutanediol are set with high pure nitrogen
After changing three times, 3 grams of new certain herbaceous plants with big flowers acid zinc are added under nitrogen protection, is heated to 160-180 degree and reacts 12 hours, be removed in vacuum unreacted
It is cooled to room temperature after raw material and obtains 313 grams of polycaprolactone polyol, passing through nuclear magnetic resonance measuring and calculating molecular weight is 3000, warp
GPC measures molecular weight distribution 1.23, hydroxyl value 36mg KOH/g.
Embodiment 3
In 3 liters of vials, 2000 grams of CL are added, 321 grams of 2,2,4,4-Tetramethyl-1,3-cyclobutanediol are set with high pure nitrogen
After changing three times, 0.2 gram of zinc oxide is added under nitrogen protection, is heated to 160-180 degree and reacts 12 hours, be removed in vacuum unreacted
It is cooled to room temperature after raw material and obtains 2320 grams of polycaprolactone polyol, passing through nuclear magnetic resonance measuring and calculating molecular weight is 1000,
Molecular weight distribution 1.30, hydroxyl value 110mg KOH/g are measured through GPC.
Embodiment 4
In 3 liters of vials, 2000 grams of CL are added, 456 grams of 2,2,4,4-Tetramethyl-1,3-cyclobutanediol are set with high pure nitrogen
After changing three times, 0.1 gram of 2 ethyl hexanoic acid zinc is added under nitrogen protection, is heated to 160-180 degree and reacts 12 hours, be removed in vacuum not
It is cooled to room temperature after the raw material of reaction and obtains 2450 grams of polycaprolactone polyol, passes through nuclear magnetic resonance measuring and calculates molecular weight and be
750, molecular weight distribution 1.16,148 mg KOH/g of hydroxyl value are measured through GPC.
Embodiment 5
In 5 liters of vials, 1560 grams of CL are added, 1440 grams of 2,2,4,4-Tetramethyl-1,3-cyclobutanediol are set with high pure nitrogen
After changing three times, 5 grams of zinc neodecanoates are added under nitrogen protection, is heated to 160-180 degree and reacts 12 hours, be removed in vacuum unreacted
It is cooled to room temperature after raw material and obtains 2980 grams of polycaprolactone polyol, passing through nuclear magnetic resonance measuring and calculating molecular weight is 300, warp
GPC measures molecular weight distribution 1.21,373 mg KOH/g of hydroxyl value.
Embodiment 6
In 3 liters of vials, 2428 grams of CL are added, 72 grams of 2,2,4,4-Tetramethyl-1,3-cyclobutanediol, use is high-purity, and vacuum is removed
It goes after unreacted raw material to be cooled to room temperature and obtains 2480 grams of polycaprolactone polyol, pass through nuclear magnetic resonance measuring and calculate molecule
Amount is 5000, measures molecular weight distribution 1.28, hydroxyl value 22mg KOH/g through GPC.
Embodiment 7
In 5 liters of vials, 3928 grams of CL are added, 72 grams of 2,2,4,4-Tetramethyl-1,3-cyclobutanediol are replaced with high pure nitrogen
After three times, 1 gram of new certain herbaceous plants with big flowers acid zinc is added under nitrogen protection, is heated to 160-180 degree and reacts 12 hours, unreacted original is removed in vacuum
It is cooled to room temperature after material and obtains 3900 grams of polycaprolactone polyol, passing through nuclear magnetic resonance measuring and calculating molecular weight is 8000, warp
GPC measures molecular weight distribution 1.29, hydroxyl value 13.8mg KOH/g.
Claims (4)
1. a kind of preparation method of novel polycaprolactone polyol, it is characterized in that using caprolactone monomer and initiator alcohol as original
Material, is reacted under the effect of the catalyst, obtains polycaprolactone polyol.
2. the method according to claim 1 for preparing polycaprolactone polyol, it is characterized in that catalyst is stannous octoate, newly
One of capric acid zinc, 2 ethyl hexanoic acid zinc and zinc oxide are used alone, dosage 0.005-10%.
3. the method according to claim 1 for preparing polycaprolactone polyol, it is characterized in that initiator alcohol refers to 2,2,4,
4- tetramethyl -1,3- cyclobutanediol, dosage are adjusted according to the size of required product molecular weight.
4. the method according to claim 1 for preparing polycaprolactone polyol, the condition of catalytic polymerization is temperature 60-180
Under degree, polymerization time is 1-24 hours, can carry out catalyst body polymerization, and solvent can also be added and carry out polymerisation in solution, carry out
Solvent is chloroform, tetrahydrofuran or toluene when polymerisation in solution.
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| CN201811112094.6A CN109265661A (en) | 2018-09-25 | 2018-09-25 | A kind of preparation method of novel polycaprolactone polyol |
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| CN201811112094.6A CN109265661A (en) | 2018-09-25 | 2018-09-25 | A kind of preparation method of novel polycaprolactone polyol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003453A (en) * | 2019-05-06 | 2019-07-12 | 青岛科技大学 | A kind of preparation method of polycaprolactone polyol |
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| CN104968716A (en) * | 2012-12-20 | 2015-10-07 | 陶氏环球技术有限责任公司 | Glycolide-based polyesters |
| PL225851B1 (en) * | 2014-07-03 | 2017-05-31 | Politechnika Warszawska | Method for producing polylactide for biomedical purposes |
| CN107073803A (en) * | 2014-07-29 | 2017-08-18 | W.L.戈尔及同仁股份有限公司 | The product for producing the method for the product formed by PLA and being manufactured by this method |
| CN109054009A (en) * | 2018-08-07 | 2018-12-21 | 四川琢新生物材料研究有限公司 | A kind of catalyst preparing polycaprolactone polyol |
| CN109265659A (en) * | 2018-09-18 | 2019-01-25 | 四川琢新生物材料研究有限公司 | A kind of catalyst preparing polycaprolactone polyol |
-
2018
- 2018-09-25 CN CN201811112094.6A patent/CN109265661A/en active Pending
Patent Citations (5)
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| CN104968716A (en) * | 2012-12-20 | 2015-10-07 | 陶氏环球技术有限责任公司 | Glycolide-based polyesters |
| PL225851B1 (en) * | 2014-07-03 | 2017-05-31 | Politechnika Warszawska | Method for producing polylactide for biomedical purposes |
| CN107073803A (en) * | 2014-07-29 | 2017-08-18 | W.L.戈尔及同仁股份有限公司 | The product for producing the method for the product formed by PLA and being manufactured by this method |
| CN109054009A (en) * | 2018-08-07 | 2018-12-21 | 四川琢新生物材料研究有限公司 | A kind of catalyst preparing polycaprolactone polyol |
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| CN110003453A (en) * | 2019-05-06 | 2019-07-12 | 青岛科技大学 | A kind of preparation method of polycaprolactone polyol |
| CN110003453B (en) * | 2019-05-06 | 2022-08-30 | 青岛科技大学 | Preparation method of polycaprolactone polyol |
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Application publication date: 20190125 |