CN105504194B - A kind of preparation method of hydrophobic thermal polyurethane resin - Google Patents
A kind of preparation method of hydrophobic thermal polyurethane resin Download PDFInfo
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/61—Polysiloxanes
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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
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6535—Compounds of group C08G18/3271
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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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
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
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Abstract
The invention discloses a kind of preparation methods of hydrophobic thermal polyurethane resin, include the following steps: modified isophorone diisocyanate and modified fluoride-containing silicone glycols after mixing, heating, heat preservation, dipropylene glycol, tartaric acid, grape sugar and acetone are added after cooling, stannous octoate is added, is heated up, heat preservation obtains first material；After first material is cooled down, then the solution containing diethanol amine He bis- (2- ethoxy) aniline is added dropwise, heats up, heat preservation obtains second material；After second material is adjusted pH to neutrality, vacuum removal acetone obtains hydrophobic thermal polyurethane resin.The hydrophobic thermal polyurethane resin of gained of the invention has excellent water-fast, heat resistance, and viscosity and elongation at break are small, and tensile strength, hardness, toughness are high.
Description
Technical field
The present invention relates to polyurethane resin technical field more particularly to a kind of preparation sides of hydrophobic thermal polyurethane resin
Method.
Background technique
Polyurethane has the structure of unique soft and hard segments block copolymer, and this give its excellent mechanical performances, and
Very wide hardness adjustable extent.These excellent comprehensive performances are not available for other a variety of commercialization rubber and plastics
's.It is that other elastomer product institutes are irreplaceable especially in soft damping application field.And existing polyurethane resin
It is often water-fast, heat resistance is not ideal enough, it is difficult to reach actual needs.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of preparation sides of hydrophobic thermal polyurethane resin
Method, the hydrophobic thermal polyurethane resin of gained has excellent water-fast, heat resistance, and viscosity and elongation at break are small, stretches strong
Degree, hardness, toughness are high.
A kind of preparation method of hydrophobic thermal polyurethane resin proposed by the present invention, includes the following steps:
S1, by modified isophorone diisocyanate and modified fluoride-containing silicone glycols after mixing, heat up, protect
Temperature is added dipropylene glycol, tartaric acid, grape sugar and acetone, adds stannous octoate after cooling, heat up, and heat preservation obtains the
One material；
S2, after first material cools down, then the solution containing diethanol amine He bis- (2- ethoxy) aniline is added dropwise, heats up, protect
Temperature obtains second material；
S3, by second material adjust pH to neutrality after, vacuum removal acetone obtains hydrophobic thermal polyurethane resin.
Preferably, modified fluoride-containing silicone glycols are prepared by following technique: by tetramethyl disiloxane and decamethyl ring
After mixing, the concentrated sulfuric acid is added dropwise in five siloxanes, and trifluoro propyl methyl cyclotrisiloxane is added dropwise in heating, and heat preservation adds after cooling
Enter sodium hydroxide and adjust pH to 6, filtering, distillation obtains material a；Tri isopropyl chlorosilane is added in methylene chloride and is uniformly mixed
Afterwards, it adds 3- methyl-3-butene-1-alcohol to stir evenly, aqueous sodium carbonate is then added dropwise, stir, stratification takes lower layer
Oily liquid is distilled to obtain material b；After mixing by material a and material b, chloroplatinic acid is added, heats up, heat preservation, vacuum is steamed
Material c is obtained after evaporating；After material c, tetrahydrofuran, tetrabutyl ammonium fluoride are mixed, temperature rising reflux, rotary evaporation obtains modification and contains
Fluorosilicone dihydric alcohol.
Preferably, in the preparation process of modified fluoride-containing silicone glycols, tetramethyl disiloxane, five silicon oxygen of decamethyl ring
Alkane, the concentrated sulfuric acid, trifluoro propyl methyl cyclotrisiloxane, tri isopropyl chlorosilane, 3- methyl-3-butene-1-alcohol, sodium carbonate are water-soluble
Liquid, chloroplatinic acid, tetrahydrofuran, tetrabutyl ammonium fluoride weight ratio be 23~26:4~7:1~1.5:10~13:6~9:2~5:
13~16:0.3~0.6:4~5:2~3.5.
Preferably, the mass fraction of the concentrated sulfuric acid is 97~100wt%, and the concentration of aqueous sodium carbonate is 0.8~1.2mol/
L。
Preferably, modified fluoride-containing silicone glycols are prepared by following technique: by tetramethyl disiloxane and decamethyl ring
After mixing, the concentrated sulfuric acid is added dropwise in five siloxanes, is warming up to 80~85 DEG C, and trifluoro propyl methyl cyclotrisiloxane, heat preservation 4 is added dropwise
~5h after cooling, be added sodium hydroxide and adjust pH to 6, filtering, distillation obtains material a；Dichloro is added in tri isopropyl chlorosilane
In methane after mixing, it adds 3- methyl-3-butene-1-alcohol to stir evenly, aqueous sodium carbonate, stirring 30 is then added dropwise
~40min, stratification take lower layer's oily liquid to be distilled to obtain material b；After mixing by material a and material b, it is added
Chloroplatinic acid is warming up to 83~86 DEG C, keeps the temperature 2~4h, material c is obtained after vacuum distillation；By material c, tetrahydrofuran, tetrabutyl fluorine
After changing ammonium mixing, temperature rising reflux, rotary evaporation obtains modified fluoride-containing silicone glycols.
Preferably, modified isophorone diisocyanate is the preparation method is as follows: by isophorone diisocyanate and 2, and 4,
The mixing of (dimethylamino methyl) phenol of 6- tri-, is passed through N2Protection, heating, keeps stirring in temperature-rise period, and heat preservation obtains material
d；After dimethyl diethoxysilane and bismuth naphthenate are mixed, it is added to the water to obtain Materialien；Material d and Materialien are mixed equal
It is even, it heats up, heat preservation, vacuum distillation obtains modified isophorone diisocyanate.
Preferably, modified isophorone diisocyanate is the preparation method is as follows: by isophorone diisocyanate and 2, and 4,
The mixing of (dimethylamino methyl) phenol of 6- tri-, is passed through N2Protection, is warming up to 85~88 DEG C, keeps stirring in temperature-rise period, protects
3~4h of temperature obtains material d；After dimethyl diethoxysilane and bismuth naphthenate are mixed, it is added to the water to obtain Materialien；By object
Expect that d and Materialien are uniformly mixed, be warming up to 50~55 DEG C, keep the temperature 2~3h, vacuum distillation obtains modified isophorone diisocyanate
Ester.
Preferably, in modified isophorone diisocyanate preparation method, isophorone diisocyanate, 2,4,6- tri-
The weight ratio of (dimethylamino methyl) phenol, dimethyl diethoxysilane and bismuth naphthenate is 22~25:1~2:3~4:0.8
~1.2.
Preferably, include the following steps:
S1, by modified isophorone diisocyanate and modified fluoride-containing silicone glycols after mixing, be warming up to 72
~75 DEG C, 2~4h is kept the temperature, dipropylene glycol, tartaric acid, grape sugar and acetone are added after being cooled to 40~50 DEG C, adds
Stannous octoate is warming up to 75~80 DEG C, and 1~4h of heat preservation obtains first material；
S2, it after first material is cooled to 30~40 DEG C, then is added dropwise molten containing diethanol amine and bis- (2- ethoxy) aniline
Liquid is warming up to 55~65 DEG C, and 0.5~1h of heat preservation obtains second material；
S3, by second material adjust pH to neutrality after, vacuum removal acetone obtains hydrophobic thermal polyurethane resin.
Preferably, include the following steps:
S1, by weight by 20~30 parts of modified isophorone diisocyanates and 60~65 parts of modified fluoride-containing siloxanes two
First alcohol after mixing, heats up, and 5~8 parts of dipropylene glycols, 0.5~0.8 part of tartaric acid, 4~5 parts are added in heat preservation after cooling
Grape sugar and acetone adds 0.1~0.2 part of stannous octoate, and heating, heat preservation obtains first material；
S2, it after first material cools down, then is added dropwise containing bis- (2- ethoxy) aniline of 3~4 parts of diethanol amine and 1~2 part
Solution, heating, heat preservation obtain second material；
S3, by second material adjust pH to neutrality after, vacuum removal acetone obtains hydrophobic thermal polyurethane resin.
Since active force is weaker between silicone molecules, poor mechanical property, the present invention is by decamethylcyclopentaandoxane and trifluoro
Hydroxypropyl methyl cyclotrisiloxane carries out ring-opening polymerisation and obtains the material a of fluorine-containing long-chain, has both polysiloxanes and Organic fluoride chemical combination
The advantages of object, molecule introduce fluoro-containing group on side chain or main chain using Si-O chain as main chain, reduce the table of entire molecule segment
Face energy, has excellent hydrophobic performance；It is reacted again with tri isopropyl chlorosilane and 3- methyl-3-butene-1-alcohol, to make
Hydroxyl in 3- methyl-3-butene-1-alcohol forms ehter bond and is protected；Then material a and material b are reacted, makes material b
In carbon-carbon double bond opening polymerize, then be deprotected original ehter bond to form hydroxyl by tetrahydrofuran, tetrabutyl ammonium fluoride
Base obtains modified fluoride-containing silicone glycols.
The present invention is by isophorone diisocyanate and 2, and after the mixing of 4,6- tri- (dimethylamino methyl) phenol, heating makes
In isophorone diisocyanate-NCO group reacts, three isocyanate groups polymerizations generate the isocyanide of six-membered ring structure
Then dimethyl diethoxysilane and bismuth naphthenate, under the action of catalyst bismuth naphthenate, diformazan is added in urea acid esters group
The sulfydryl that the hydrolysis of base diethoxy silane generates is reacted with the isocyanate group on isophorone diisocyanate trimer,
Make polysiloxane grafted on isophorone diisocyanate trimer, lays the groundwork for the preparation of hydrophobic thermal polyurethane resin.
The present invention is prepared hydrophobic heat-resisting using modified isophorone diisocyanate and modified fluoride-containing silicone glycols
Polyurethane resin introduces side-chain branching and fluorinated polysiloxane segment on polyurethane structural, makes hydrophobic thermal polyurethane resin
Viscosity and elongation at break it is small, also improve tensile strength of the invention, hardness, toughness；Modified isophorone diisocyanate
There is isocyanuric acid ester hexatomic ring and organosilicon radical simultaneously on ester, wherein isocyanuric acid ester hexatomic ring is imitated with strong electrophilic
It answers, the C=N bond polarity of-NCO in molecule is caused to increase, improve reactivity, accelerate modified isophorone diisocyanate
With the reaction speed of hydroxyl, the degree of cross linking is improved, the hardness and adhesive force of hydrophobic thermal polyurethane resin are improved；Hydrophobic resistance to hot polymerization
Silicon atom, fluorine atom in urethane resin make lipophilic group arrange outward to air, hydrophilic group is inside easily to surface migration, enrichment
Arrangement reduces surface tension and surface energy so that contact angle increases, and makes shipwreck to soak in its surface spreading, to mention
High water resistance of the invention, heat resistance；And hydroxyl there are five containing in glucose molecule, it can be reacted with-NCO, generation has
The polyurethane of cross-linked structure, molecular chain movement are restricted, and crosslinking is so that intermolecular gap becomes smaller on a large scale, moisture
Son is difficult to enter inside polyurethane molecular, and the water absorption rate for showing as resin constantly declines, and water resistance improves, and the introducing of glucose makes
It obtains urethane crosslinks degree to increase, cohesive energy becomes larger, and improves thermal stability and hardness of the invention.
Hydrophobic thermal polyurethane resin of the invention has excellent water-fast, heat resistance, and viscosity and elongation at break
Small, tensile strength, hardness, toughness are high.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of preparation method of hydrophobic thermal polyurethane resin proposed by the present invention, includes the following steps:
S1,20 parts of modified isophorone diisocyanates and 65 parts of modified fluoride-containing silicone glycols are mixed by weight
After uniformly, 72 DEG C are warming up to, keeps the temperature 4h, 8 parts of dipropylene glycols, 0.5 part of tartaric acid, 5 portions of grapes are added after being cooled to 40 DEG C
Sugar and acetone adds 0.1 part of stannous octoate, is warming up to 80 DEG C, heat preservation 1h obtains first material；
S2, it after first material is cooled to 40 DEG C, then is added dropwise containing bis- (2- ethoxy) aniline of 3 parts of diethanol amine and 2 parts
Solution is warming up to 55 DEG C, and heat preservation 1h obtains second material；
S3, by second material adjust pH to neutrality after, vacuum removal acetone obtains hydrophobic thermal polyurethane resin.
Modified fluoride-containing silicone glycols are prepared by following technique: by weight by 26 parts of tetramethyl disiloxanes and 4 parts
Decamethylcyclopentaandoxane after mixing, is added dropwise the concentrated sulfuric acid that mass fraction is 100wt%, is warming up to 80 DEG C, be added dropwise 13 parts
Trifluoro propyl methyl cyclotrisiloxane keeps the temperature 4h, after cooling, sodium hydroxide is added and adjusts pH to 6, filtering, distillation obtains material
a；9 parts of tri isopropyl chlorosilanes are added in methylene chloride after mixing, 2 parts of 3- methyl-3-butene-1-alcohol stirrings are added
Uniformly, the aqueous sodium carbonate that 16 parts of concentration are 0.8mol/L is then added dropwise, stirs 40min, stratification takes lower layer's oily liquid
It is distilled to obtain material b；After mixing by material a and material b, 0.3 part of chloroplatinic acid is added, is warming up to 86 DEG C, keeps the temperature 2h,
Material c is obtained after vacuum distillation；After material c, 5 parts of tetrahydrofurans, 2 parts of tetrabutyl ammonium fluorides are mixed, temperature rising reflux, rotation is steamed
Hair obtains modified fluoride-containing silicone glycols.
Modified isophorone diisocyanate the preparation method is as follows: by weight by 25 parts of isophorone diisocyanate and
1 part 2, the mixing of 4,6- tri- (dimethylamino methyl) phenol is passed through N2Protection, is warming up to 88 DEG C, keeps stirring in temperature-rise period,
Heat preservation 3h obtains material d；After 4 parts of dimethyl diethoxysilanes and 0.8 part of bismuth naphthenate are mixed, it is added to the water to obtain material
e；Material d and Materialien are uniformly mixed, are warming up to 55 DEG C, keeps the temperature 2h, vacuum distillation obtains modified isophorone diisocyanate
Ester.
Embodiment 2
A kind of preparation method of hydrophobic thermal polyurethane resin proposed by the present invention, includes the following steps:
S1,30 parts of modified isophorone diisocyanates and 60 parts of modified fluoride-containing silicone glycols are mixed by weight
After uniformly, 75 DEG C are warming up to, keeps the temperature 2h, 5 parts of dipropylene glycols, 0.8 part of tartaric acid, 4 portions of grapes are added after being cooled to 50 DEG C
Sugar and acetone adds 0.2 part of stannous octoate, is warming up to 75 DEG C, heat preservation 4h obtains first material；
S2, it after first material is cooled to 30 DEG C, then is added dropwise containing bis- (2- ethoxy) aniline of 4 parts of diethanol amine and 1 part
Solution is warming up to 65 DEG C, and heat preservation 0.5h obtains second material；
S3, by second material adjust pH to neutrality after, vacuum removal acetone obtains hydrophobic thermal polyurethane resin.
Modified fluoride-containing silicone glycols are prepared by following technique: by weight by 23 parts of tetramethyl disiloxanes and 7 parts
Decamethylcyclopentaandoxane after mixing, is added dropwise the concentrated sulfuric acid that mass fraction is 97wt%, is warming up to 85 DEG C, be added dropwise 10 part three
Fluoropropyl methyl cyclotrisiloxane keeps the temperature 5h, after cooling, sodium hydroxide is added and adjusts pH to 6, filtering, distillation obtains material a；
6 parts of tri isopropyl chlorosilanes are added in methylene chloride after mixing, it is equal to add 5 parts of 3- methyl-3-butene-1-alcohol stirrings
It is even, the aqueous sodium carbonate that 13 parts of concentration are 1.2mol/L is then added dropwise, stirs 30min, stratification, take lower layer's oily liquid into
Row distillation obtains material b；After mixing by material a and material b, 0.6 part of chloroplatinic acid is added, is warming up to 83 DEG C, keeps the temperature 4h, very
Material c is obtained after sky distillation；After material c, 4 parts of tetrahydrofurans, 3.5 parts of tetrabutyl ammonium fluorides are mixed, temperature rising reflux, rotation is steamed
Hair obtains modified fluoride-containing silicone glycols.
Modified isophorone diisocyanate the preparation method is as follows: by weight by 22 parts of isophorone diisocyanate and
2 part 2, the mixing of 4,6- tri- (dimethylamino methyl) phenol is passed through N2Protection, is warming up to 85 DEG C, keeps stirring in temperature-rise period,
Heat preservation 4h obtains material d；After 3 parts of dimethyl diethoxysilanes and 1.2 parts of bismuth naphthenates are mixed, it is added to the water to obtain material
e；Material d and Materialien are uniformly mixed, are warming up to 50 DEG C, keeps the temperature 3h, vacuum distillation obtains modified isophorone diisocyanate
Ester.
Embodiment 3
A kind of preparation method of hydrophobic thermal polyurethane resin proposed by the present invention, includes the following steps:
S1,22 parts of modified isophorone diisocyanates and 63 parts of modified fluoride-containing silicone glycols are mixed by weight
After uniformly, 73 DEG C are warming up to, keeps the temperature 3h, 7 parts of dipropylene glycols, 0.6 part of tartaric acid, 4.8 parts of Portugals are added after being cooled to 42 DEG C
Grape sugar and acetone adds 0.15 part of stannous octoate, is warming up to 78 DEG C, heat preservation 2h obtains first material；
S2, it after first material is cooled to 36 DEG C, then is added dropwise containing bis- (2- ethoxy) benzene of 3.3 parts of diethanol amine and 1.8 parts
The solution of amine is warming up to 58 DEG C, and heat preservation 0.8h obtains second material；
S3, by second material adjust pH to neutrality after, vacuum removal acetone obtains hydrophobic thermal polyurethane resin.
Modified fluoride-containing silicone glycols are prepared by following technique: by weight by 25 parts of tetramethyl disiloxanes and 5 parts
Decamethylcyclopentaandoxane after mixing, is added dropwise the concentrated sulfuric acid that mass fraction is 99wt%, is warming up to 82 DEG C, be added dropwise 12 part three
Fluoropropyl methyl cyclotrisiloxane keeps the temperature 4.3h, after cooling, sodium hydroxide is added and adjusts pH to 6, filtering, distillation obtains material
a；8 parts of tri isopropyl chlorosilanes are added in methylene chloride after mixing, 3 parts of 3- methyl-3-butene-1-alcohol stirrings are added
Uniformly, the aqueous sodium carbonate that 15 parts of concentration are 0.9mol/L is then added dropwise, stirs 38min, stratification takes lower layer's oily liquid
It is distilled to obtain material b；After mixing by material a and material b, 0.4 part of chloroplatinic acid is added, is warming up to 85 DEG C, keeps the temperature 3h,
Material c is obtained after vacuum distillation；After material c, 4.8 parts of tetrahydrofurans, 2.5 parts of tetrabutyl ammonium fluorides are mixed, temperature rising reflux, rotation
Turn evaporation and obtains modified fluoride-containing silicone glycols.
Modified isophorone diisocyanate the preparation method is as follows: by weight by 24 parts of isophorone diisocyanate and
1.2 part 2, the mixing of 4,6- tri- (dimethylamino methyl) phenol is passed through N2Protection, is warming up to 87 DEG C, does not stop to stir in temperature-rise period
It mixes, heat preservation 3.3h obtains material d；After 3.8 parts of dimethyl diethoxysilanes and 1 part of bismuth naphthenate are mixed, it is added to the water
To Materialien；Material d and Materialien are uniformly mixed, are warming up to 54 DEG C, keeps the temperature 2.2h, vacuum distillation obtains modified isophorone two
Isocyanates.
Embodiment 4
A kind of preparation method of hydrophobic thermal polyurethane resin proposed by the present invention, includes the following steps:
S1,28 parts of modified isophorone diisocyanates and 62 parts of modified fluoride-containing silicone glycols are mixed by weight
After uniformly, 74 DEG C are warming up to, keeps the temperature 2.5h, 6 parts of dipropylene glycols, 0.7 part of tartaric acid, 4.5 parts are added after being cooled to 46 DEG C
Grape sugar and acetone adds 0.18 part of stannous octoate, is warming up to 77 DEG C, heat preservation 3h obtains first material；
S2, it after first material is cooled to 32 DEG C, then is added dropwise containing bis- (2- ethoxy) benzene of 3.5 parts of diethanol amine and 1.5 parts
The solution of amine is warming up to 62 DEG C, and heat preservation 0.6h obtains second material；
S3, by second material adjust pH to neutrality after, vacuum removal acetone obtains hydrophobic thermal polyurethane resin.
Modified fluoride-containing silicone glycols are prepared by following technique: by weight by 24 parts of tetramethyl disiloxanes and 6 parts
Decamethylcyclopentaandoxane after mixing, is added dropwise the concentrated sulfuric acid that mass fraction is 98wt%, is warming up to 83 DEG C, be added dropwise 11 part three
Fluoropropyl methyl cyclotrisiloxane keeps the temperature 4.5h, after cooling, sodium hydroxide is added and adjusts pH to 6, filtering, distillation obtains material
a；7 parts of tri isopropyl chlorosilanes are added in methylene chloride after mixing, 4 parts of 3- methyl-3-butene-1-alcohol stirrings are added
Uniformly, the aqueous sodium carbonate that 14 parts of concentration are 1mol/L is then added dropwise, stirs 33min, stratification, take lower layer's oily liquid into
Row distillation obtains material b；After mixing by material a and material b, 0.5 part of chloroplatinic acid is added, is warming up to 84 DEG C, keeps the temperature 3.5h,
Material c is obtained after vacuum distillation；After material c, 4.5 parts of tetrahydrofurans, 3 parts of tetrabutyl ammonium fluorides are mixed, temperature rising reflux, rotation
Evaporation obtains modified fluoride-containing silicone glycols.
Modified isophorone diisocyanate the preparation method is as follows: by weight by 23 parts of isophorone diisocyanate and
1.5 part 2, the mixing of 4,6- tri- (dimethylamino methyl) phenol is passed through N2Protection, is warming up to 86 DEG C, does not stop to stir in temperature-rise period
It mixes, heat preservation 3.6h obtains material d；After 3.5 parts of dimethyl diethoxysilanes and 1.1 parts of bismuth naphthenates are mixed, it is added to the water
Obtain Materialien；Material d and Materialien are uniformly mixed, are warming up to 52 DEG C, keeps the temperature 2.5h, vacuum distillation obtains modified isophorone
Diisocyanate.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of hydrophobic thermal polyurethane resin, which comprises the steps of:
S1, by modified isophorone diisocyanate and modified fluoride-containing silicone glycols after mixing, heat up, keep the temperature, drop
Dipropylene glycol, tartaric acid, grape sugar and acetone are added after temperature, adds stannous octoate, heats up, heat preservation obtains the first object
Material；
S2, after first material cools down, then the solution containing diethanol amine He bis- (2- ethoxy) aniline is added dropwise, heats up, keeps the temperature
To second material；
S3, by second material adjust pH to neutrality after, vacuum removal acetone obtains hydrophobic thermal polyurethane resin；
Modified fluoride-containing silicone glycols are prepared by following technique: tetramethyl disiloxane and decamethylcyclopentaandoxane are mixed
After uniformly, the concentrated sulfuric acid is added dropwise, trifluoro propyl methyl cyclotrisiloxane is added dropwise in heating, and after cooling, sodium hydroxide tune is added in heat preservation
PH to 6, filtering are saved, distillation obtains material a；Tri isopropyl chlorosilane is added in methylene chloride after mixing, 3- is added
Methyl-3-butene-1-alcohol stirs evenly, and aqueous sodium carbonate is then added dropwise, stirring, and stratification takes lower layer's oily liquid to carry out
Distillation obtains material b；After mixing by material a and material b, chloroplatinic acid is added, heats up, heat preservation obtains object after vacuum distillation
Expect c；After material c, tetrahydrofuran, tetrabutyl ammonium fluoride are mixed, temperature rising reflux, rotary evaporation obtains modified fluoride-containing siloxanes two
First alcohol；
Modified isophorone diisocyanate is the preparation method is as follows: by isophorone diisocyanate and (the diformazan ammonia of 2,4,6- tri-
Ylmethyl) phenol mixing, it is passed through N2Protection, heating, keeps stirring in temperature-rise period, and heat preservation obtains material d；By dimethyl two
After Ethoxysilane and bismuth naphthenate mixing, it is added to the water to obtain Materialien；Material d and Materialien are uniformly mixed, heated up, is protected
Temperature, vacuum distillation obtain modified isophorone diisocyanate.
2. the preparation method of hydrophobic thermal polyurethane resin according to claim 1, which is characterized in that modified fluoride-containing siloxanes
In the preparation process of dihydric alcohol, tetramethyl disiloxane, decamethylcyclopentaandoxane, the concentrated sulfuric acid, three silicon of trifluoro propyl methyl ring
Oxygen alkane, tri isopropyl chlorosilane, 3- methyl-3-butene-1-alcohol, aqueous sodium carbonate, chloroplatinic acid, tetrahydrofuran, tetrabutyl fluorine
Change ammonium weight ratio be 23~26:4~7:1~1.5:10~13:6~9:2~5:13~16:0.3~0.6:4~5:2~
3.5。
3. the preparation method of hydrophobic thermal polyurethane resin according to claim 1 or claim 2, which is characterized in that the matter of the concentrated sulfuric acid
Amount score is 97~100wt%, and the concentration of aqueous sodium carbonate is 0.8~1.2mol/L.
4. the preparation method of hydrophobic thermal polyurethane resin according to claim 1 or claim 2, which is characterized in that modified fluoride-containing silicon
Oxygen alkane dihydric alcohol is prepared by following technique: after mixing by tetramethyl disiloxane and decamethylcyclopentaandoxane, being added dropwise dense
Sulfuric acid is warming up to 80~85 DEG C, and trifluoro propyl methyl cyclotrisiloxane is added dropwise, and keeps the temperature 4~5h, and after cooling, sodium hydroxide is added
PH to 6, filtering are adjusted, distillation obtains material a；Tri isopropyl chlorosilane is added in methylene chloride after mixing, is added
3- methyl-3-butene-1-alcohol stirs evenly, and aqueous sodium carbonate is then added dropwise, and stirs 30~40min, and stratification takes lower layer
Oily liquid is distilled to obtain material b；After mixing by material a and material b, chloroplatinic acid is added, is warming up to 83~86 DEG C, protects
2~4h of temperature, obtains material c after vacuum distillation；After material c, tetrahydrofuran, tetrabutyl ammonium fluoride are mixed, temperature rising reflux, rotation
Evaporation obtains modified fluoride-containing silicone glycols.
5. the preparation method of hydrophobic thermal polyurethane resin according to claim 1, which is characterized in that modified isophorone two
Isocyanates is the preparation method is as follows: by isophorone diisocyanate and 2, the mixing of 4,6- tri- (dimethylamino methyl) phenol is led to
Enter N2Protection, is warming up to 85~88 DEG C, keeps stirring in temperature-rise period, and 3~4h of heat preservation obtains material d；By dimethyl diethyl
After oxysilane and bismuth naphthenate mixing, it is added to the water to obtain Materialien；Material d and Materialien are uniformly mixed, it is warming up to 50~
55 DEG C, 2~3h is kept the temperature, vacuum distillation obtains modified isophorone diisocyanate.
6. according to claim 1 or the preparation method of the 5 hydrophobic thermal polyurethane resins, which is characterized in that modified different Fo Er
In ketone diisocyanate preparation method, isophorone diisocyanate, 2,4,6- tri- (dimethylamino methyl) phenol, dimethyl two
The weight ratio of Ethoxysilane and bismuth naphthenate is 22~25:1~2:3~4:0.8~1.2.
7. the preparation method of hydrophobic thermal polyurethane resin according to claim 1 or claim 2, which is characterized in that including walking as follows
It is rapid:
S1, by modified isophorone diisocyanate and modified fluoride-containing silicone glycols after mixing, be warming up to 72~75
DEG C, 2~4h is kept the temperature, dipropylene glycol, tartaric acid, grape sugar and acetone are added after being cooled to 40~50 DEG C, adds octanoic acid
Stannous is warming up to 75~80 DEG C, and 1~4h of heat preservation obtains first material；
S2, after first material is cooled to 30~40 DEG C, then the solution containing diethanol amine He bis- (2- ethoxy) aniline is added dropwise, rises
For temperature to 55~65 DEG C, 0.5~1h of heat preservation obtains second material；
S3, by second material adjust pH to neutrality after, vacuum removal acetone obtains hydrophobic thermal polyurethane resin.
8. the preparation method of hydrophobic thermal polyurethane resin according to claim 1 or claim 2, which is characterized in that including walking as follows
It is rapid:
S1, by weight by 20~30 parts of modified isophorone diisocyanates and 60~65 parts of modified fluoride-containing silicone glycols
After mixing, it heats up, 5~8 parts of dipropylene glycols, 0.5~0.8 part of tartaric acid, 4~5 portions of grapes are added in heat preservation after cooling
Sugar and acetone adds 0.1~0.2 part of stannous octoate, and heating, heat preservation obtains first material；
S2, after first material cools down, then the solution containing bis- (2- ethoxy) aniline of 3~4 parts of diethanol amine and 1~2 part is added dropwise,
Heating, heat preservation obtain second material；
S3, by second material adjust pH to neutrality after, vacuum removal acetone obtains hydrophobic thermal polyurethane resin.
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