CN100526366C - Polytetrafuran-base block polyether diol and its preparing method - Google Patents
Polytetrafuran-base block polyether diol and its preparing method Download PDFInfo
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- CN100526366C CN100526366C CNB2006100983164A CN200610098316A CN100526366C CN 100526366 C CN100526366 C CN 100526366C CN B2006100983164 A CNB2006100983164 A CN B2006100983164A CN 200610098316 A CN200610098316 A CN 200610098316A CN 100526366 C CN100526366 C CN 100526366C
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- base block
- propylene oxide
- block polyether
- dibasic alcohol
- polytetrahydrofuran
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Abstract
The polytetrafuran-base block polyether diol features its structural general expression of HO-[A1]a1-[CH2CH2CH2CH2O]n-[A2]a2-H, where, the structure unit A1 is CH(CH3)CH2O, CH(CH3)CH2OCH2CH2O or other ether structure, A2 is CH2CH(CH3)O, CH2CH2OCH2CH(CH3)O or other ether structure, a1 is the number of structure unit A1, a2 is the number of structure unit A2, a1 is near to or the same as a2, each of a1 and a2 is 1-35, and n is number of [CH2CH2CH2CH2O] and equal to 2-30. The polytetrafuran-base block polyether diol is liquid, has convenient use and low production cost, and may be used in preparing polyurethane with excellent performance similar to that of polytetrahydrofuran.
Description
Technical field
The present invention relates to high performance polyurethane and use the polyether glycol field, exactly the goods that made by the PTMEG-PPG polyether Glycols can be used for fields such as water miscible liquid, elastomerics, coating, seal gum, tackiness agent.
Background technology
It makes the physical and chemical performance of polyurethane products decisions such as the kind of polyvalent alcohols such as polyester polyol, PTMEG, polycarbonate diol, Aethoxy Sklerol, functionality, molecular weight, molecular structure, so the status of polyvalent alcohol in synthesizing formula just seems extremely important.And the excellent properties of the polyurethane product that polytetrahydrofuran (PTMEG) makes, its polyurethane product hardness height, wear resistance are good.Also obtain simultaneously everybody generally acknowledging, but polytetrahydrofuran normal temperature is solid-state, causes using inconvenience, and cost an arm and a leg, most producers that produce urethane are hung back.Polytetrahydrofuran base polyether Glycols is liquid, and easy to use, preparation cost is relatively low.Be raw material with tetrahydrofuran (THF)-propylene oxide (or oxyethane) random copolymerization ether in the world at present, when the character of similar urethane with polytetrahydrofuran preparation and high-performance being arranged with the urethane of its preparation, found that also its polyurethane product is used for aqueous polyurethane new purposes such as film, wherein aqueous wooden ware is coated with membrane product and has characteristics such as hardness height, strong adhesion, wear resistance be good.But technology controlling and process is comparatively complicated in the preparation process of tetrahydrofuran (THF)-propylene oxide (or oxyethane) random copolymerization ether.With the polytetrahydrofuran is that polymerizable raw material propylene oxide (or oxyethane) synthetic polytetrahydrofuran base block polyether dibasic alcohol synthesis technique is simple relatively, constant product quality.Be similar to the character and the high-performance of the urethane for preparing with random copolymerization ether with the polyurethanes of its preparation.
Summary of the invention
The purpose of this invention is to provide a kind of based on polytetrahydrofuran, easy to use, that production cost is lower liquid Aethoxy Sklerol and method for making thereof.
The invention provides novel linear molecule chain structure compound polytetrahydrofuran base block polyether dibasic alcohol (being PTMEG-PPG) of a series of block structures and preparation method thereof, we have carried out screening and modification to catalyzer, have synthesized a series of PTMEG base block polyether dibasic alcohol.
Technical scheme of the present invention is as follows:
A kind of polytetrahydrofuran base block polyether dibasic alcohol, it has following general structure:
HO-[A
1]
a1-[CH
2CH
2CH
2CH
2O]
n-[A
2]
a2H (I)
Wherein: modular construction A
1Expression is CH (CH
3) CH
2O or CH (CH
3) CH
2OCH
2CH
2Ethers structures such as O, A
2Expression is CH
2CH (CH
3) O or CH
2CH
2OCH
2CH (CH
3) ethers structure such as O, a1 or a2 represent modular construction [CH (CH
3) CH
2O], [CH (CH
3) CH
2OCH
2CH
2O], CH
2CH (CH
3) O or CH
2CH
2OCH
2CH (CH
3) number of O, a1 is close with a2 or identical, and a1 and a2 are 1-300, preferably 1-35; N represents modular construction [CH
2CH
2CH
2CH
2O] number, n=2-100; Preferred n=2-30.
Polytetrahydrofuran base block polyether dibasic alcohol of the present invention, also can be at the two ends of general formula (I) shack oxidative ethane primary hydroxyl end-blocking again, have following general structure:
HO-[B]
b1[A
1]
a1-[CH
2CH
2CH
2CH
2O]n-[A
2]
a2[B]
b2H (II)
Wherein: modular construction A
1Expression is CH (CH
3) CH
2O, CH (CH
3) CH
2OCH
2CH
2Ethers structures such as O, A
2Expression is CH
2CH (CH
3) O, CH
2CH
2OCH
2CH (CH
3) ethers structure such as O, a1, a2 are close or identical, expression modular construction [CH (CH
3) CH
2O], [CH (CH
3) CH
2OCH
2CH
2O], [CH
2CH (CH
3) O] or [CH
2CH
2OCH
2CH (CH
3) O] and number, a1, a2 are 1-300,1-35 preferably, modular construction B represents CH
2CH
2O ethers structure, b1, b2 are close or identical, expression modular construction [CH
2CH
2O] number, between 1-20, preferably between 1-10;
In a kind of preparation
The method of polytetrahydrofuran base block polyether dibasic alcohol, it is
The 30-500 mass parts polymerization degree is polytetrahydrofuran (n=2-30) and the catalyst mix of 2-30, under whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 
Change for several times, logical 90-140 ℃ of elder generation
The mixture of the propylene oxide of about 30-50 mass parts or propylene oxide and oxyethane, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
Total amount is the mixture of the remaining propylene oxide of about 30-1200 mass parts or propylene oxide and oxyethane, has led to aging for some time of back, vacuum
Remove unreacted propylene oxide or oxyethane and small molecules, cooling discharge gets required polytetrahydrofuran base block polyether dibasic alcohol (I), institute
Catalyzer can be mixture, phosphonitrile class catalyzer or the potassium hydroxide of bimetallic catalyst and protonic acid.
On
The method for making of the end capped polytetrahydrofuran base block polyether of primary hydroxyl dibasic alcohol, it is
On
Method synthetic polytetrahydrofuran base block polyether dibasic alcohol (I) 50-500 mass parts is mixed with phosphonitrile class catalyzer or potassium hydroxide, stirs
Under the state after 120-130 ℃ of coupling vacuum stripping, N
2 
Change for several times, logical 90-140 ℃ of elder generation
The oxyethane of about 5-50 mass parts, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
Total amount is the remaining oxyethane of about 30-100 mass parts, has led to aging for some time of back, and is true
Remove unreacted propylene oxide or oxyethane and small molecules, cooling discharge gets the end capped polytetrahydrofuran base block polyether of required primary hydroxyl dibasic alcohol (II).
Polytetrahydrofuran base block polyether dibasic alcohol of the present invention is liquid, and easy to use, preparation cost is relatively low, and the character and the high-performance of similar urethane with polytetrahydrofuran preparation arranged with the urethane of its preparation.With polytetrahydrofuran base block polyether dibasic alcohol of the present invention and isophorone diisocyanate (IPDI) and tolylene diisocyanate (TDI) etc. is raw material, its sticking power of polyurethane coating film goods and the glossiness that make under catalyst action also are significantly increased, tensile strength increases, and toughness improves.
Description of drawings
Fig. 1 is the synthetic PTMEG-PPG of a polymerization catalyst propylene oxide institute pure ether polymer for embodiment 1 usefulness DMC
1The H-NMR collection of illustrative plates;
Fig. 2 is the IR collection of illustrative plates of the synthetic PTMEG-PPG of polymerization catalyst propylene oxide institute alcohol ether polymer for embodiment 1 usefulness DMC.
Concrete real-time mode
In order to be illustrated more clearly in the present invention, be listed below embodiment, but protection scope of the present invention is not had any restriction.
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 1000 PTMEG as initiator 100g, with 0.01g dmc catalyst (model: MMC 2005.10.11, Research Inst. of Jinling Petrochemical Co. of SINOPEC, together following) and 0.001g sulfuric acid mixing, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 
Change for several times, logical 140 ℃ of elder generations
About propylene oxide 50g, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
Remaining propylene oxide (100g altogether) is aged to-0.1MPa (reacting kettle inner pressure, down together) after having led to, true
Remove unreacted propylene oxide and small molecules, cooling discharge gets required PTMEG-PPG polyether Glycols.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 56.1mgKOH/g; Moisture content: 0.05%.
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 162 PTMEG as initiator 100g,
0.006g dmc catalyst and 0.001g phosphoric acid mixing stir
Under the state after 120-130 ℃ of coupling vacuum stripping, N
2 Change for several times, logical at 140 ℃
Propylene oxide 35g is aged to after having led to-0.1MPa, and is true
Remove unreacted propylene oxide and small molecules, cooling discharge gets required PTMEG-PPG polyether Glycols.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 513mgKOH/g; Moisture content: 0.05%.
Embodiment 3
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 162 PTMEG as initiator 100g, with 0.08g dmc catalyst and 0.001g acetic acid mixing, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 
Change for several times, logical 120 ℃ of elder generations
About the mixture of propylene oxide and oxyethane (the PO/EO ratio is 1/1) 30g, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
Be total to the remaining propylene oxide of 63g and the mixture of oxyethane, be aged to after having led to-0.1MPa, true
Remove unreacted propylene oxide and small molecules, cooling discharge gets required PTMEG-PPG polyether Glycols.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 425mgKOH/g; Moisture content: 0.05%.
Embodiment 4
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 162 PTMEG as initiator 100g, with 0.027g dmc catalyst and 0.001g sulfuric acid mixing, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 Change for several times, logical 140 ℃ of elder generations
About propylene oxide 50g, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
The remaining propylene oxide of 1260g is aged to after having led to-0.1MPa altogether, and is true
Remove unreacted propylene oxide and small molecules, cooling discharge gets required PTMEG-PPG polyether Glycols.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 51.0mgKOH/g; Moisture content: 0.05%.
Embodiment 5
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 162 PTMEG as initiator 50g, with 0.06g dmc catalyst and 0.001g sulfuric acid mixing, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 Change for several times, logical 140 ℃ of elder generations
About the mixture of propylene oxide and oxyethane (the PO/EO ratio is 1/1) 50g, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
Be total to the remaining propylene oxide of 1100g and the mixture of oxyethane, be aged to after having led to-0.1MPa, true
Remove unreacted propylene oxide and small molecules, cooling discharge gets required PTMEG-PPG polyether Glycols.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 30.1mgKOH/g; Moisture content: 0.05%.
Embodiment 6
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 2200 PTMEG as initiator 440g, with 0.023g dmc catalyst and 0.0005g sulfuric acid mixing, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 
Change for several times, logical at 140 ℃
The mixture of propylene oxide and oxyethane (the PO/EO ratio is 1/1, altogether 22g) is aged to after having led to-0.1MPa, and is true
Remove unreacted propylene oxide and small molecules, cooling discharge gets required PTMEG-PPG polyether Glycols.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 30.1mgKOH/g; Moisture content: 0.05%.
Embodiment 7
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 2200 PTMEG as initiator 220g, with 0.021g dmc catalyst and 0.002g sulfuric acid mixing, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 Change for several times, logical 140 ℃ of elder generations
About propylene oxide 50g, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
The remaining propylene oxide of 200g is aged to after having led to-0.1MPa altogether, and is true
Remove unreacted propylene oxide and small molecules, cooling discharge gets required PTMEG-PPG polyether Glycols.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 26.7mgKOH/g; Moisture content: 0.05%.
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 2200 PTMEG as initiator 220g, with 0.029g dmc catalyst and 0.001g sulfuric acid mixing, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 Change for several times, logical 140 ℃ of elder generations
About the mixture of propylene oxide and oxyethane (the PO/EO ratio is 1/1) 50g, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
Be total to the remaining propylene oxide of 360g and the mixture of oxyethane, be aged to after having led to-0.1MPa, true
Remove unreacted propylene oxide and small molecules, cooling discharge gets required PTMEG-PPG polyether Glycols.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 19.4mgKOH/g; Moisture content: 0.05%.
Embodiment 9
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 1000 PTMEG as initiator 100g, with 0.2g KOH catalyzer mixing, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 Change for several times, logical at 140 ℃
Propylene oxide 100g is aged to after having led to-0.1MPa, and is true
Remove unreacted propylene oxide and small molecules, cooling discharge gets required PTMEG-PPG polyether Glycols.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 56.1mgKOH/g; Moisture content: 0.05%.
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 1000 PTMEG as initiator 100g,
0.14g phosphonitrile catalyzer mixing, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 Change for several times, logical 120 ℃ of elder generations
About the mixture of propylene oxide and oxyethane (the PO/EO ratio is 1/1) 50g, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
Be total to the remaining propylene oxide of 360g and the mixture of oxyethane, be aged to after having led to-0.1MPa, true
Remove unreacted propylene oxide and small molecules, cooling discharge gets required PTMEG-PPG polyether Glycols.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 24.4mgKOH/g; Moisture content: 0.05%.
Embodiment 11
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 1000 PTMEG as initiator 100g,
0.015g dmc catalyst and 0.001g sulfuric acid mixing, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 Change for several times, logical down at 140 ℃
About propylene oxide 50g, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
The remaining propylene oxide of 100g is aged to after having led to-0.1MPa altogether, and is true
Remove unreacted propylene oxide and small molecules, then in the synthetic polyethers, add
0.6g the KOH catalyzer, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 Change for several times, logical down in certain temperature and pressure
Oxyethane 5g is aged to after having led to-0.1MPa, and is true
Remove unreacted propylene oxide and small molecules, cooling discharge gets the end capped PTMEG-PPG polyether Glycols of required primary hydroxyl.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 54.7mgKOH/g; Moisture content: 0.05%.
Embodiment 12
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 1000 PTMEG as initiator 100g, with 0.015g dmc catalyst and 0.001g sulfuric acid mixing, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 
Change for several times, logical down at 140 ℃
About propylene oxide 50g, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
The remaining propylene oxide of 100g is aged to after having led to-0.1MPa altogether, and is true
Remove unreacted propylene oxide and small molecules, then in the synthetic polyethers, add
0.14g the phosphonitrile catalyzer, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 Change for several times, logical down in certain temperature and pressure
Oxyethane, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
The remaining oxyethane of 45g is aged to after having led to-0.1MPa altogether, and is true
Remove unreacted propylene oxide and small molecules, cooling discharge gets the end capped PTMEG-PPG polyether Glycols of required primary hydroxyl.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 45.8mgKOH/g; Moisture content: 0.05%.
Embodiment 13
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 1000 PTMEG as initiator 100g, with 0.05g phosphonitrile catalyzer mixing, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 Change for several times, logical down at 140 ℃
About the mixture of propylene oxide and oxyethane (the PO/EO ratio is 1/1) 50g, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
The remaining propylene oxide and the mixture of oxyethane (360g altogether) are aged to after having led to-0.1MPa, and be true
Remove unreacted propylene oxide and small molecules, then in the synthetic polyethers, add
2.5g the KOH catalyzer, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 Change for several times, logical down in certain temperature and pressure
Oxyethane 44g is aged to after having led to-0.1MPa, and is true
Remove unreacted propylene oxide and small molecules cooling discharge and get required PTMEG-PPG polyether Glycols.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 22.3mgKOH/g; Moisture content: 0.05%.
Embodiment 14
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 1000 PTMEG as initiator 100g,
0.75g KOH catalyzer mixing stirs
Under the state after 120-130 ℃ of coupling vacuum stripping, N
2 Change for several times, logical down at 90 ℃
The mixture of propylene oxide and oxyethane (the PO/EO ratio is 1/1) 100g is aged to after having led to-0.1MPa, and is true
Remove unreacted propylene oxide and small molecules, then under certain temperature and pressure, continue logical
Oxyethane 45g is aged to after having led to-0.1MPa, and is true
Remove unreacted propylene oxide and small molecules, cooling discharge gets required PTMEG-PPG polyether Glycols.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 45.8mgKOH/g; Moisture content: 0.05%.
Embodiment 15
In 2L dried and clean stainless steel cauldron, take by weighing molecular weight Mn and be 1000 PTMEG as initiator 100g,
0.08g phosphonitrile catalyzer mixing, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2 
Change for several times, logical down at 140 ℃
About the mixture of propylene oxide and oxyethane (the PO/EO ratio is 1/1) 50g, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
The remaining propylene oxide and the mixture of oxyethane (100g altogether) are aged to after having led to-0.1MPa, and be true
Remove unreacted propylene oxide and small molecules, then under certain temperature and pressure, continue logical
Oxyethane, the temperature fast rise also in reactor
When having pressure obviously to descend, continue logical
Remaining 45g is aged to after having led to-0.1MPa, and is true
Remove unreacted propylene oxide and small molecules, cooling discharge gets required PTMEG-PPG polyether Glycols.
Gained PTMEG-PPG polyether Glycols performance index:
Hydroxyl value: 45.8mgKOH/g; Moisture content: 0.05%.
Emulsion is synthetic
In be equipped with agitator, thermometer,
Add in the four-hole boiling flask of the clean dried of pipe with fixed attention
(embodiment 1 preparation 100g), under the whipped state, is warming up to 115-125 ℃ very to the PTMEG-PPG polyether Glycols
Water 1.5hr is cooled to 40-50 ℃, adds
Quantitatively the ethylene glycol of (4g) adds
Isophorone diisocyanate (IPDI) (20g) and tolylene diisocyanate (TDI) mixture (15g) slowly is warming up to reaction about 90 ℃, and about 5hr reaches design load to NCO% content.Cooling adds
By dimethyl formamide (DMF) dissolved dimethylol propionic acid (DMPA6), survey NCO% content in 80 ℃ of about 3hr of reaction and reach design load.Add
Hydroxyethyl methylacrylate (10g) and acetone (50g) are surveyed NCO% in the 50-55 ℃ of about 3hr of reaction and are reached design load.Be cooled to about 30 ℃,
The gained prepolymer solution moves under the dispersion machine, adds
In the triethylamine (5g) and about 3Min, add under the high-speed stirring state
Most of deionized water (25-30 ℃) disperses after 10 seconds, again
Speed
The part deionized water that is dissolved with quadrol adds
, disperse behind the 30Min the emulsion of oyster white blueing light.It is true to heat up
Go to get the water-based emulsion dispersion behind most of DMF and the acetone.Again
Wetting agent,
Mixture such as infusion, flow agent (0.2g, the mass ratio of three components are 1:1:1) slowly adds
In the water-based emulsion dispersion under the whipped state, behind the dispersed with stirring 30min water-borne wood coating.(the performance perameter of polyether Glycols: hydroxyl value, 56 ± 2mgKOH/g; Moisture content, 0.05%; Viscosity, 600mps/25 ℃; Unsaturated double-bond content, 0.007mmol/g) The performance test results of synthetic water-borne wood coating is as follows:
Outward appearance: oyster white blueing light liquid;
Solid content: 35%; PH value :～8.5;
The emulsion film performance:
Pencil hardness: 2H;
Sticking power (cross-hatching): 1 grade;
Wear resistance: 0.0068g.
Claims (8)
1. polytetrahydrofuran base block polyether dibasic alcohol is characterized in that it has following general structure:
HO-[A
1]
A1-[CH
2CH
2CH
2CH
2O]
n-[A
2]
A2-H is wherein: modular construction A
1Expression CH (CH
3) CH
2O or CH (CH
3) CH
2OCH
2CH
2O ethers structure, A
2Expression is CH
2CH (CH
3) O or CH
2CH
2OCH
2CH (CH
3) O ethers structure, a1 represents modular construction [CH (CH
3) CH
2O] or [CH (CH
3) CH
2OCH
2CH
2O] number, a2 represents modular construction [CH (CH
3) CH
2O] or [CH
2CH
2OCH
2CH (CH
3) O] and number, a1 is close or identical with the numerical value of a2, a1 and a2 are 1-300, n represents modular construction [CH
2CH
2CH
2CH
2O] number, n=2-30.
2. polytetrahydrofuran base block polyether dibasic alcohol according to claim 1 is characterized in that: a1 and a2 are 1-35.
3. polytetrahydrofuran base block polyether dibasic alcohol according to claim 1 is characterized in that: at the two ends of the described general formula of the claim 1 end capped polytetrahydrofuran base block polyether of primary hydroxyl dibasic alcohol, have following general structure:
HO-[B]
b1[A
1]
a1-[CH
2CH
2CH
2CH
2O]
n-[A
2]
a2[B]
b2H
Wherein: modular construction B represents CH
2CH
2O ethers structure, b1 is close or identical with the numerical value of b2, expression modular construction [CH
2CH
2O] number, b1 and b2 are 1-20; Modular construction A
1Expression is CH (CH
3) CH
2O or CH (CH
3) CH
2OCH
2CH
2O ethers structure, unit A
2Expression is CH
2CH (CH
3) O or CH
2CH
2OCH
2CH (CH
3) O ethers structure, a1 represents modular construction [CH (CH
3) CH
2O] or [CH (CH
3) CH
2OCH
2CH
2O] number, a2 represents modular construction [CH
2CH (CH
3) O] or [CH
2CH
2OCH
2CH (CH
3) O] and number, a1 is close with a2 or identical, a1 and a2 are 1-300.
4. polytetrahydrofuran base block polyether dibasic alcohol according to claim 3 is characterized in that: b1 and b2 are 1-10; A1 and a2 are 1-35.
5. method for preparing the described polytetrahydrofuran base block polyether of claim 1 dibasic alcohol, it is characterized in that: it is to be polytetrahydrofuran and the catalyst mix of 2-30 with the 30-500 mass parts polymerization degree, under whipped state after 120-130 ℃ of coupling vacuum stripping, N2 replaces for several times, feed the propylene oxide of about 30-50 mass parts or the mixture of propylene oxide and oxyethane earlier at 90-140 ℃, when obviously descending when temperature fast rise in the reactor and with pressure, continuing to feed total amount is the mixture of the remaining propylene oxide of 30-1200 mass parts or propylene oxide and oxyethane, it is aging to have led to the back, the unreacted propylene oxide of vacuum removal or oxyethane and small molecules, cooling discharge get required polytetrahydrofuran base block polyether dibasic alcohol.
6. the method for making of polytetrahydrofuran base block polyether dibasic alcohol according to claim 5 is characterized in that: described catalyzer is mixture, phosphonitrile class catalyzer or the potassium hydroxide of bimetallic catalyst and protonic acid.
7. the method for making of polytetrahydrofuran base block polyether dibasic alcohol according to claim 6 is characterized in that described protonic acid is sulfuric acid, phosphoric acid, acetic acid.
8. method for preparing the described polytetrahydrofuran base block polyether of claim 3 dibasic alcohol, it is characterized in that: it is that the described method synthetic of claim 5 polytetrahydrofuran base block polyether dibasic alcohol 50-500 mass parts is mixed with phosphonitrile class catalyzer or potassium hydroxide, under the whipped state after 120-130 ℃ of coupling vacuum stripping, N
2Displacement for several times, at 90-140 ℃ of oxyethane that feeds about 5-50 mass parts earlier, when obviously descending when temperature fast rise in the reactor and with pressure, continuing to feed total amount is the remaining oxyethane of about 30-100 mass parts, it is aging to have led to the back, the unreacted propylene oxide of vacuum removal or oxyethane and small molecules, cooling discharge get the end capped polytetrahydrofuran base block polyether of required primary hydroxyl dibasic alcohol.
Priority Applications (1)
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| FR2924433B1 (en) * | 2007-12-04 | 2010-09-03 | Snpe Materiaux Energetiques | MULTIPURPOSE HTPE COPOLYMERS BASED ON PTHF; THEIR SYNTHESIS AND USE. |
| DE102008020980A1 (en) * | 2008-04-25 | 2009-10-29 | Henkel Ag & Co. Kgaa | Curable compositions containing silylated polyurethanes based on polyether block polymers |
| DE102010001470A1 (en) * | 2010-02-02 | 2011-08-04 | Henkel AG & Co. KGaA, 40589 | Polyether block copolymers and compositions obtainable therefrom |
| CN112048047B (en) * | 2020-08-24 | 2022-05-10 | 郑州大学 | Transparent yellowing-resistant high-toughness self-repairing polyurethane elastomer based on hydrogen bonding pyridine |
| CN112940239A (en) * | 2021-04-12 | 2021-06-11 | 山东蓝星东大有限公司 | Preparation method of hybrid block polyether polyol |
| CN113788940A (en) * | 2021-09-30 | 2021-12-14 | 中国石油化工股份有限公司 | Preparation method of polytetrahydrofuran polypropylene oxide block copolyether |
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| US4705830A (en) * | 1984-05-29 | 1987-11-10 | Toa Nenryo Kogyo Kabushiki Kaisha | Block copolymer containing tetrahydrofuran block |
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| US5773207A (en) * | 1996-01-09 | 1998-06-30 | Imation Corp. | Photographic emulsions |
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| US3523144A (en) * | 1967-03-01 | 1970-08-04 | Minnesota Mining & Mfg | Block copolymers of tetrahydrofuran and process for their preparation |
| US4705830A (en) * | 1984-05-29 | 1987-11-10 | Toa Nenryo Kogyo Kabushiki Kaisha | Block copolymer containing tetrahydrofuran block |
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