CN108084423A - A kind of preparation method for increase-volume chain extension material - Google Patents
A kind of preparation method for increase-volume chain extension material Download PDFInfo
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- CN108084423A CN108084423A CN201711131595.4A CN201711131595A CN108084423A CN 108084423 A CN108084423 A CN 108084423A CN 201711131595 A CN201711131595 A CN 201711131595A CN 108084423 A CN108084423 A CN 108084423A
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- increase
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- caprolactone
- epsilon
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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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- 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
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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)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of preparation methods for increase-volume chain extension material.By weight, in a kettle add in poly epsilon caprolactone lactone, 2,3,5,6 tetrahydroxy, 2,5 cyclohexadiene Isosorbide-5-Nitrae diketone, tridecanol polyoxyethylene ether, divinyl stannous chloride, 2 isocyanic acids, the third 2 e pioic acid methyl ester, dichloro (2,6,10, ten bromine triolefins, 1,12 diyl) ruthenium, water heats up, reaction, and product is filtered, washing, it is dry to get to polyurethane chain-expanding agent product.
Description
Technical field
The present invention relates to a kind of preparation methods of chain-expanding agent, especially a kind of preparation side for increase-volume chain extension material
Method.
Background technology
Polyurethane material is the current best thermal insulation material of performance in the world.Main chain is containing-NHCOO-constitutional repeating unit
A kind of polymer.English abbreviation PU.By isocyanates（Monomer）It is polymerized with hydroxy compounds.Due to containing highly polar
Carbamate groups insoluble in non-polar group, has good oil resistivity, toughness, wearability, resistance to ag(e)ing and adhesiveness.
Adaptation wide temperature range can be made with different material（- 50~150 DEG C）Material, including elastomer, thermoplastic resin and
Thermosetting resin.Not hydrolysis under high temperature, also not alkali-proof medium.Chain extender refers to that molecule chain extension, the change of extension can be promoted
Close object.It is mainly the chemicals of difunctional in the generation of polyether polyols.It is added in polyurethane products production process
Chain extender is conducive to the mechanical property of reinforcing polyurethane product.
CN104151494A discloses a kind of epoxy chain extenders and preparation method thereof, in parts by weight, by 22-27
Part gamma carotene is added in along butadiene acid anhydrides in organic solvents with 9-11 parts, solid-liquid ratio 31:60-38:60g/ml；It is fully mixed
Close uniform, the generation D-A reactions 3-5h under 130-170 DEG C, nitrogen protection；90-95 parts are added in into the mixture after reaction again
Epoxychloropropane and 0.6-0.8 parts of amine bromides, are heated to reflux 5-7h, after being subsequently cooled to 65-75 DEG C, add in excessive hydroxide
Sodium, it is washed to obtain finished product.The epoxy chain extenders of the present invention can be applied to the recycling of polyester, polyamide-based engineering plastics, with
And biodegradable polymers material property improves, raw materials and reagents derives from a wealth of sources, of low cost, and reaction condition is mild, production
Especially suitable for large-scale industrial production, the long molecule of high-purity can be made in the easily separated purifying of object efficiently, in high yield
Chain, macromolecule multi-epoxy functional group chain extender.
CN102936307A discloses a kind of for biology base and the epoxy-functional chain extension of biodegradable based polyalcohol
Agent, epoxy-functional chain extender preparation method and applications, the chain extender are made of (by mass fraction) following composition of raw materials：It is poly-
6-caprolactone class monomer：50~75；Glycerol acrylate class monomer：25~50；Initiator：2~12.Epoxy-functional chain extender
Preparation method include selecting above-mentioned reaction monomers and initiator, reaction kettle is added according to the order of setting, in appropriate temperature
It is copolymerized under degree and mixing speed, reactor product is after removing solvent, granulation into product.
Existing chain-expanding agent product, although the higher long chain of purity can be made, unimolecule interchain linkage compared with
Weak, the shock resistance of resin material is weaker.
The content of the invention
The purpose of the present invention is：There is provided a kind of preparation method for increase-volume chain extension material, it is characterised in that preparation process
Including：
By weight, poly-epsilon-caprolactone is added in a kettle, 2,3,5,6- tetrahydroxy -2,5- cyclohexadienes-Isosorbide-5-Nitrae-diketone,
Tridecanol polyoxyethylene ether, divinyl stannous chloride, 2- isocyanic acid propyl- 2- e pioic acid methyl esters, dichloro (2,6,10, ten bromine triolefins-
1,12- diyl) ruthenium, water is warming up to 70-80 DEG C, reacts 6-12h, and product is filtered, washing, dry to get to polyurethane increase-volume
Chain extender product.
Described 2,3,5,6- tetrahydroxy -2,5- cyclohexadienes-Isosorbide-5-Nitrae-diketone, quality dosage are the 3- of poly-epsilon-caprolactone
8%。
The tridecanol polyoxyethylene ether, quality dosage are the 1-3% of poly-epsilon-caprolactone.
The divinyl stannous chloride, quality dosage are the 0.1-0.5% of poly-epsilon-caprolactone.
The 2- isocyanic acid propyl- 2- e pioic acid methyl esters, quality dosage are the 0.5-1.5% of poly-epsilon-caprolactone.
Described dichloro (2,6,10, ten bromine triolefin -1, the 12- diyls) ruthenium, quality dosage are poly-epsilon-caprolactone
0.01-0.1%。
The water, quality dosage are the 400-800% of poly-epsilon-caprolactone.
The poly-epsilon-caprolactone, 2,3,5,6- tetrahydroxy -2,5- cyclohexadienes-Isosorbide-5-Nitrae-diketone, tridecanol polyoxyethylene
Ether, divinyl stannous chloride, 2- isocyanic acid propyl- 2- e pioic acid methyl esters, dichloro (2,6,10, ten bromine triolefin -1,12- diyls) ruthenium
It is commercial product.
The product of the present invention has the advantages that：
The polyurethane chain-expanding agent product that the present invention is produced is easy to disperse in synthesis of polyurethane system, produces polyurethane
Product extent of polymerization is uniform；Strong for the single-stranded branching of high polymer, crosslinked action is good, while ensureing to extend bending performance
Improve the impact resistance of polyurethane products.
Specific embodiment
Embodiment 1
In a kettle, poly-epsilon-caprolactone 100Kg, 2,3,5,6- tetrahydroxy -2,5- cyclohexadiene-Isosorbide-5-Nitrae-diketone 5.5Kg are added in,
Tridecanol polyoxyethylene ether 2Kg, divinyl stannous chloride 0.3Kg, 2- isocyanic acid propyl- 2- e pioic acid methyl ester 1Kg, dichloro (2,6,
10, ten bromine triolefin -1,12- diyls) ruthenium 0.05Kg, water 600Kg, 75 DEG C are warming up to, reacts 9h, product is filtered, washes, and does
It is dry to get to polyurethane chain-expanding agent product.
Embodiment 2
In a kettle, poly-epsilon-caprolactone 100Kg is added in, 2,3,5,6- tetrahydroxy -2,5- cyclohexadiene-Isosorbide-5-Nitrae-diketone 3Kg, ten
Triol polyoxyethylene ether 1Kg, divinyl stannous chloride 0.1Kg, 2- isocyanic acid propyl- 2- e pioic acid methyl ester 0.5Kg, dichloro (2,6,
10, ten bromine triolefin -1,12- diyls) ruthenium 0.01Kg, water 400Kg, 70 DEG C are warming up to, reacts 6h, product is filtered, washes, and does
It is dry to get to polyurethane chain-expanding agent product.
Embodiment 3
In a kettle, poly-epsilon-caprolactone 100Kg is added in, 2,3,5,6- tetrahydroxy -2,5- cyclohexadiene-Isosorbide-5-Nitrae-diketone 8Kg, ten
Triol polyoxyethylene ether 3Kg, divinyl stannous chloride 0.5Kg, 2- isocyanic acid propyl- 2- e pioic acid methyl ester 1.5Kg, dichloro (2,6,
10, ten bromine triolefin -1,12- diyls) ruthenium 0.1Kg, water 800Kg, 80 DEG C are warming up to, reacts 12h, product is filtered, washes, and does
It is dry to get to polyurethane chain-expanding agent product.
Comparative example 1
Tridecanol polyoxyethylene ether is added without, other conditions are the same as embodiment 1.
Comparative example 2
Divinyl stannous chloride is added without, other conditions are the same as embodiment 1.
Comparative example 3
2- isocyanic acid propyl- 2- e pioic acid methyl esters are added without, other conditions are the same as embodiment 1.
Comparative example 4
Dichloro (2,6,10, ten bromine triolefin -1,12- diyls) ruthenium is added without, other conditions are the same as embodiment 1.
Embodiment 4
The chain extender product of embodiment 1-3 and comparative example 1-4 are added to when preparing polyurethane resin in polyurethane resin, added
Enter 3.5% that amount is polyurethane resin, reference standard GB/T1049-1993 detects the shock strength of mixture, calculates shock strength
Increase rate is shown in Table 1：
Table 1：Comparison of the chain extender that different process is made to polyurethane resin shock strength increase rate.
Claims (7)
1. a kind of preparation method for increase-volume chain extension material, it is characterised in that include the following steps：
By weight, poly-epsilon-caprolactone is added in a kettle, 2,3,5,6- tetrahydroxy -2,5- cyclohexadienes-Isosorbide-5-Nitrae-diketone,
Tridecanol polyoxyethylene ether, divinyl stannous chloride, 2- isocyanic acid propyl- 2- e pioic acid methyl esters, dichloro (2,6,10, ten bromine triolefins-
1,12- diyl) ruthenium, water is warming up to 70-80 DEG C, reacts 6-12h, and product is filtered, washing, dry to get to polyurethane increase-volume
Chain extender product.
2. a kind of preparation method for increase-volume chain extension material according to claim 1, it is characterised in that：Described 2,3,
5,6- tetrahydroxy -2,5- cyclohexadienes-Isosorbide-5-Nitrae-diketone, quality dosage are the 3-8% of poly-epsilon-caprolactone.
3. a kind of preparation method for increase-volume chain extension material according to claim 1, it is characterised in that：Described 13
Alcohol polyoxyethylene ether, quality dosage are the 1-3% of poly-epsilon-caprolactone.
4. a kind of preparation method for increase-volume chain extension material according to claim 1, it is characterised in that：The diethyl
Alkenyl stannous chloride, quality dosage are the 0.1-0.5% of poly-epsilon-caprolactone.
5. a kind of preparation method for increase-volume chain extension material according to claim 1, it is characterised in that：The 2- is different
Cyanic acid propyl- 2- e pioic acid methyl esters, quality dosage are the 0.5-1.5% of poly-epsilon-caprolactone.
6. a kind of preparation method for increase-volume chain extension material according to claim 1, it is characterised in that：The dichloro
(2,6,10, ten bromine triolefin -1,12- diyls) ruthenium, quality dosage are the 0.01-0.1% of poly-epsilon-caprolactone.
7. a kind of preparation method for increase-volume chain extension material according to claim 1, it is characterised in that：The water,
Its quality dosage is the 400-800% of poly-epsilon-caprolactone.
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| CN201711131595.4A CN108084423A (en) | 2017-11-15 | 2017-11-15 | A kind of preparation method for increase-volume chain extension material |
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| CN201711131595.4A CN108084423A (en) | 2017-11-15 | 2017-11-15 | A kind of preparation method for increase-volume chain extension material |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4891417A (en) * | 1986-12-15 | 1990-01-02 | Ausimont S.R.L. | Epoxy resins prepared from perfluoroalkylene telomers |
| CN1413239A (en) * | 1999-12-23 | 2003-04-23 | 阿克佐诺贝尔股份有限公司 | Aqueous coating composition comprising addition polymer and polyurethane |
| US20110060105A1 (en) * | 2007-12-20 | 2011-03-10 | Nanoresins Ag | Modified phenol resins |
| CN103214668A (en) * | 2013-05-09 | 2013-07-24 | 东华大学 | Preparation method of chain extender for waterborne polyurethane |
| CN105859975A (en) * | 2016-06-19 | 2016-08-17 | 王金明 | Preparation method of capacity-increasing chain extender with core-shell structure |
-
2017
- 2017-11-15 CN CN201711131595.4A patent/CN108084423A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4891417A (en) * | 1986-12-15 | 1990-01-02 | Ausimont S.R.L. | Epoxy resins prepared from perfluoroalkylene telomers |
| CN1413239A (en) * | 1999-12-23 | 2003-04-23 | 阿克佐诺贝尔股份有限公司 | Aqueous coating composition comprising addition polymer and polyurethane |
| US20110060105A1 (en) * | 2007-12-20 | 2011-03-10 | Nanoresins Ag | Modified phenol resins |
| CN103214668A (en) * | 2013-05-09 | 2013-07-24 | 东华大学 | Preparation method of chain extender for waterborne polyurethane |
| CN105859975A (en) * | 2016-06-19 | 2016-08-17 | 王金明 | Preparation method of capacity-increasing chain extender with core-shell structure |
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Application publication date: 20180529 |