CN107936216A - A kind of organic-silicon-modified Isocyanate prepolymers body of no-solvent type use for synthetic leather and preparation method thereof - Google Patents

A kind of organic-silicon-modified Isocyanate prepolymers body of no-solvent type use for synthetic leather and preparation method thereof Download PDF

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CN107936216A
CN107936216A CN201711323525.9A CN201711323525A CN107936216A CN 107936216 A CN107936216 A CN 107936216A CN 201711323525 A CN201711323525 A CN 201711323525A CN 107936216 A CN107936216 A CN 107936216A
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silicon
methyl phenyl
synthetic leather
phenyl silicone
organic
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CN107936216B (en
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温荣政
董火成
赵修文
曹敏
孙嘉鹏
李宁
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Liming Research Institute of Chemical Industry Co Ltd
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Liming Research Institute of Chemical Industry Co Ltd
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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
    • 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
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/0045—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by applying a ready-made foam layer; obtained by compressing, crinkling or crushing a foam layer, e.g. Kaschierverfahren für Schaumschicht
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/142—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of polyurethanes with other resins in the same layer
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used

Abstract

The invention discloses organic-silicon-modified Isocyanate prepolymers body of a kind of no-solvent type use for synthetic leather and preparation method thereof, the performed polymer contains following structural compounds：Wherein, R is aryl or fat-based；A, b is natural number.Preparation method comprises the following steps：(1) octamethylcy-clotetrasiloxane, tetramethyl tetraphenyl cyclotetrasiloxane and acidic catalyst are added into reactor, then tetramethyldihydrogendisiloxane is added, at 60~80 DEG C, 4~6h of ring-opening polymerization, cooling, neutralize, washing, filtering, removing small molecule by-product, obtain the methyl phenyl silicone of end hydrogen-based end-blocking；(2) by the end hydrogen-based methyl phenyl silicone obtained in step (1) and allyl amine in H2PtCl6Reacted under catalyst, the methyl phenyl silicone of Amino End Group end-blocking is made；(3) step (2) product is dehydrated, and then reacts the performed polymer that generation end group is NCO with isocyanate-monomer again.

Description

A kind of organic-silicon-modified Isocyanate prepolymers body of no-solvent type use for synthetic leather and its preparation Method
Technical field
The invention belongs to uninanned platform to remove from office field, and in particular to it is organic-silicon-modified that one kind prepares no-solvent type use for synthetic leather Isocyanate prepolymers body and preparation method thereof.
Background technology
Polyurethane (PU) synthetic leather is the artificial leather produced with PU resins with base fabric.Traditional synthetic leather is mainly solvent-borne type Synthetic leather, its solvent are mostly the volatile dimethylformamide of low boiling point, toluene, acetone and other organic solvent, these solvent accountings Reach 70%~80%, and can't recycle completely at present, not only environment is polluted, but also cause body to damage employee Evil, has an effect on product quality.With the increase for the environmental protection pressure that solvent borne polyurethane synthetic leather faces, exploitation is more green to gather Urethane synthetic leather method is extremely urgent.
The processing of no-solvent type Synthetic Leather uses solvent-free polyurethane resin to replace solvent type resin to lead to for raw material Cross new tanning production line and leather finished product is made, its production technology is mixed by the way that isocyanate component and polyol component are filled into Syncephalon, then by injection, coating release liners, into baking oven crosslinking curing, patch when resin semi-solid preparation, cures, winding Get product.Solvent-free polyurethane resin is free of poisonous Organic chemical solvents, to environment non-hazardous, reaches the height of ecological, environmental protective It is required that.But its breathable moisture permeability of uninanned platform leather product is all poor, influences its appearance, pleasant softness, this is mainly Because it is in hole-closing structure that uninanned platform, which removes from office abscess in the intumescent coating to be formed,.Therefore, improving Synthetic Leather, it is ventilative saturating It is moist to have great importance.
Patent document CN 106087451A disclose a kind of preparation method of air-permeable synthetic leather, by preparing polyethers amino Silicon oil modified polyurethane, then adds auxiliary agent, coating, solidification, washing and drying prepare air previous polyurethane artificial leather, but it is prepared Process water amount is big, and washing and drying, which cures, needs 2~3h, and hardening time length, the method has pollution environment and production efficiency Low shortcoming, the synthetic leather gas permeability of preparation reach 725ml/cm2H, penetrability 962g/m2·24h.Patent document CN 104558494 A disclose a kind of high moisture-inhibiting modified polyurethane and preparation method thereof, synthetic leather surface layer resin are prepared, using pre-polymerization The method for closing processing solves double hydroxyl alkyl polysiloxanes and polyether polyol problem of phase separation, but prepares organic-silicon-modified poly- ammonia Ester still needs to use a large amount of organic solvents, can not solve the problems, such as solvent contamination.
Although above method can make some performances of polyurethane improve or change by organic silicon modified polyurethane, still In the presence of be unfavorable for environmental protection, breathable moisture permeability do not reach requirement the shortcomings of.
The content of the invention
The invention solves first technical problem be to provide a kind of organic-silicon-modified isocyanide of no-solvent type use for synthetic leather Acid esters performed polymer, the performed polymer structure contain methyl phenyl silicone, and the performed polymer is as isocyanate component and hydroxyl group Distribution is closed, and can assign the more preferable pleasant softness of Synthetic Leather and breathable moisture permeability.
The invention solves second technical problem be to provide a kind of organic-silicon-modified isocyanic acid of uninanned platform leather The preparation method of ester performed polymer, this method is from molecular structure modification, by synthesizing double-end amino methyl phenyl silicone, Generation performed polymer is reacted with isocyanates.
To solve first technical problem, the present invention provides a kind of organic-silicon-modified isocyanates of no-solvent type use for synthetic leather Performed polymer, contains following structural compounds：
Wherein, R is aryl or fat-based, and carbon number is preferably 6~13；A, b is natural number.
To solve second technical problem, the technical scheme is that：It is organic that one kind prepares no-solvent type use for synthetic leather The method of Si modification Isocyanate prepolymers body, comprises the following steps：
(1) octamethylcy-clotetrasiloxane, tetramethyl tetraphenyl cyclotetrasiloxane and acidic catalyst are added into reactor, so After add tetramethyldihydrogendisiloxane, at 60~80 DEG C, 4~6h of ring-opening polymerization, after reaction, cooling, reaction production For thing alkali neutralization to neutrality, washing, filtering, removing small molecule by-product, obtain the methyl phenyl silicone of end hydrogen-based end-blocking. Rotary Evaporators removing small molecule by-product can be used, revolving temperature is advisable for 100~130 DEG C.
(2) by the end hydrogen-based methyl phenyl silicone obtained in step (1) and allyl amine under H2PtCl6 catalyst Reaction, is made the methyl phenyl silicone of Amino End Group end-blocking.Reaction temperature is generally 50~60 DEG C, and the reaction time is generally 3 ~5h；Used catalyst H2PtCl6 dosages are generally 10/1000000ths~the 30 of two kinds of reactant qualities.
(3) product obtained in step (2) is carried out dehydrating, then reacts generation end group with isocyanate-monomer again For the performed polymer of NCO.
Step (1) described acidic catalyst is preferably that concentrated hydrochloric acid, the concentrated sulfuric acid, trifluoromethanesulfonic acid or acid cation exchange tree One kind or composition in fat etc., the more preferably concentrated sulfuric acid.
The dosage of acidic catalyst used is generally the 1%~3% of two kinds of cyclosiloxane quality in step (1).Acidity is urged Preferably 30~40min of first hybrid reaction after agent addition system, then adds tetramethyldihydrogendisiloxane and block instead Should.
As the preferred solution of the present invention, the number for the methyl phenyl silicone that the end hydrogen-based of design blocks in step (1) Average molecular weight is 500~4000, is preferably 1000~3000, and product viscosity mistake should not be made in production performed polymer process by being based primarily upon Height, and pliability is moderate.
As the preferred solution of the present invention, the isocyanate-monomer in step (3) is isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), At least one of benzene dimethylene diisocyanate (XDI) or Methylcyclohexyl diisocyanate (HTDI) etc., it is further excellent Elect isophorone diisocyanate (IPDI) and methyl diphenylene diisocyanate (MDI) as.
The present invention provides organic-silicon-modified Isocyanate prepolymers body of a kind of no-solvent type use for synthetic leather and preparation method thereof, Performed polymer as the isocyanate component for preparing Synthetic Leather, due in strand silicone segments have it is excellent submissive Property and gas permeability, can assign Synthetic Leather has excellent feel compliance and moisture-penetrable ventilated energy.Preparation method of the present invention, Without solvent, safety and environmental protection is pollution-free, and technique is simple.
Embodiment
With reference to embodiments, the present invention will be described in further detail.
Embodiment 1
(1) 100g octamethylcy-clotetrasiloxanes are weighed and 61g tetramethyl tetraphenyl cyclotetrasiloxanes are added to temperature In the three-necked flask of meter and condensation reflux unit, N2Protection, is warming up to 60 DEG C, adds the 4.83g concentrated sulfuric acids, stirring reaction 30min, adds 7.5g tetramethyldihydrogendisiloxanes, and stirring reaction 5h, after reaction, is cooled to room temperature at 60 DEG C, Using sodium acid carbonate neutralization reaction liquid to neutrality, wash, filtering, small molecule is evaporated off using Rotary Evaporators in 130 DEG C of backspins Accessory substance, rotates 4h, is filtered under diminished pressure, and the methyl phenyl silicone for the end hydrogen-based end-blocking that number-average molecular weight is 3000 is made.
(2) methyl phenyl silicone and 3.8g allyl amines for weighing the end hydrogen-based end-blocking that 100g steps (1) obtain add Enter in reactor, be warming up to 50 DEG C, add 0.001g H2PtCl6Catalyst, reacts 4h, prepares the aminomethyl phenyl of Amino End Group end-blocking Polysiloxanes.
(3) methyl phenyl silicone that the Amino End Group that step (2) obtains blocks first is heated to 120 DEG C, decompression carries out Dehydration 4h, it is stand-by.Into reactor add 100g isophorone diisocyanate, then by constant pressure funnel to its The methyl phenyl silicone of middle dropwise addition 128g Amino End Groups end-blocking, controlling reaction temperature react 4h at 70 DEG C, measure reaction product The content of NCO is 14.6%, that is, obtains organic-silicon-modified isocyanate prepolymer.
Embodiment 2
(1) 100g octamethylcy-clotetrasiloxanes are weighed and 57.5g tetramethyl tetraphenyl cyclotetrasiloxanes are added to reactor In, 80 DEG C are warming up to, adds the 3.15g concentrated sulfuric acids, stirring reaction 40min, adds 11.3g tetramethyldihydrogendisiloxanes, Stirring reaction 5h, after reaction, is cooled to room temperature, neutrality is neutralized to using Sodium bicarbonate at 80 DEG C, washes, and filtering, is adopted Small molecule by-product is evaporated off in 130 DEG C of backspins with Rotary Evaporators, rotates 4h, is filtered under diminished pressure, number-average molecular weight is prepared For the methyl phenyl silicone of 2000 end hydrogen-based end-blocking.
(2) weigh 100g ends hydrogen methyl phenyl silicone and 5.7g allyl amines are added in reactor, be warming up to 60 DEG C, add 0.002g H2PtCl6Catalyst, reacts 4h, prepares the methyl phenyl silicone of Amino End Group end-blocking.
(3) to 120 DEG C, decompression carries out the methyl phenyl silicone room temperature that the Amino End Group for first obtaining step (2) blocks Dehydration 4h, it is stand-by.Into three-necked flask add 100g isophorone diisocyanate, controlling reaction temperature at 70 DEG C, Then 118g ends aminomethyl phenyl based polysiloxane is added dropwise into flask by constant pressure funnel, reacts 4h, measures reaction product The content of NCO is 14.8%, that is, obtains organic-silicon-modified isocyanate prepolymer.
Embodiment 3
(1) 100g octamethylcy-clotetrasiloxanes are weighed and 46g tetramethyl tetraphenyl cyclotetrasiloxanes are added to reactor, are risen Temperature adds the 4.38g concentrated sulfuric acids, stirring reaction 30min, adds 22.6g tetramethyldihydrogendisiloxanes, at 75 DEG C to 75 DEG C Lower stirring reaction 5h, after reaction, is cooled to room temperature, neutrality is neutralized to using sodium acid carbonate, wash, filtering, using rotation Small molecule by-product is evaporated off in 130 DEG C of backspins in evaporimeter, rotates 4h, is filtered under diminished pressure, and number-average molecular weight is prepared as 1000 End hydrogen-based end-blocking methyl phenyl silicone.
(2) methyl phenyl silicone and 7.6g allyl amines for weighing 100g ends hydrogen-based end-blocking are added in reactor, 60 DEG C are warming up to, adds 0.003g H2PtCl6Catalyst, reacts 4h, prepares the methyl phenyl silicone of Amino End Group end-blocking.
(3) methyl phenyl silicone that the Amino End Group that step 2 obtains blocks first is heated to 120 DEG C, decompression is taken off Water process 4h, it is stand-by.The isophorone diisocyanate of 100g is added into three-necked flask, controlling reaction temperature is at 70 DEG C, so The methyl phenyl silicone of 97.4g Amino End Groups end-blocking is added dropwise into flask by constant pressure funnel afterwards, reacts 4h, measure is anti- The content for answering product NCO is 14.5%, that is, obtains organic-silicon-modified isocyanate prepolymer.
Embodiment 4
(1) 100g octamethylcy-clotetrasiloxanes are weighed and 61g tetramethyl tetraphenyl cyclotetrasiloxanes are added in reactor, 60 DEG C are warming up to, adds the 3.22g concentrated sulfuric acids, stirring reaction 30min, adds 11.3g tetramethyldihydrogendisiloxanes, 60 Stirring reaction 5h, after reaction, is cooled to room temperature, neutrality is neutralized to using sodium acid carbonate at DEG C, washes, filtering, using rotation Turn evaporimeter and small molecule by-product is evaporated off in 130 DEG C of backspins, rotate 4h, be filtered under diminished pressure, number-average molecular weight, which is prepared, is The methyl phenyl silicone of 3000 end hydrogen-based end-blocking.
(2) methyl phenyl silicone and 5.7g allyl amines for weighing 100g ends hydrogen-based end-blocking are added in reactor, 50 DEG C are warming up to, adds 0.001g H2PtCl6Catalyst, reacts 4h, prepares the methyl phenyl silicone of Amino End Group end-blocking.
(3) methyl phenyl silicone that the Amino End Group that step 2 obtains blocks is heated to 120 DEG C, decompression is dehydrated 4h is handled, it is stand-by.The toluene di-isocyanate(TDI) of 100g is added into three-necked flask, then controlling reaction temperature passes through at 70 DEG C The methyl phenyl silicone of 104g Amino End Groups end-blocking is added dropwise into flask for constant pressure funnel, reacts 4h, measures reaction product The content of NCO is 14.8%, that is, obtains organic-silicon-modified isocyanate prepolymer.
Embodiment 5
(1) 100g octamethylcy-clotetrasiloxanes are weighed and 46g tetramethyl tetraphenyl cyclotetrasiloxanes are added to temperature In the three-necked flask of meter and condensation reflux unit, it is placed in oil bath pan, N2Protection, is warming up to 80 DEG C, adds the dense sulphur of 2.92g Acid, stirring reaction 40min, adds 22.6g tetramethyldihydrogendisiloxanes, the stirring reaction 5h at 80 DEG C, after reaction, Room temperature is cooled to, neutrality is neutralized to using sodium acid carbonate, is washed, filtering, is evaporated off in 130 DEG C of backspins small using Rotary Evaporators Lecular by-products, rotate 5h, are filtered under diminished pressure, and the poly- silicon of aminomethyl phenyl for the end hydrogen-based end-blocking that number-average molecular weight is 1000 is prepared Oxygen alkane.
(2) methyl phenyl silicone and 5.7g allyl amines for weighing 100g ends hydrogen-based end-blocking are added to thermometer In the three-necked flask of condensation reflux unit, it is placed in oil bath pan, is warming up to 70 DEG C, adds 0.002g H2PtCl6Catalyst, 4h is reacted, prepares the methyl phenyl silicone of Amino End Group end-blocking.
(3) methyl phenyl silicone that the Amino End Group that step 2 obtains blocks is heated to 120 DEG C in three-necked flask, Decompression is carried out dehydrating 4h, stand-by.The toluene di-isocyanate(TDI) of 100g is added into three-necked flask, controlling reaction temperature is 70 DEG C, the methyl phenyl silicone of 79.4g Amino End Groups end-blocking is then added dropwise into flask by constant pressure funnel, reacts 4h, The content for measuring reaction product NCO is 14.7%, that is, obtains organic-silicon-modified isocyanate prepolymer.
No-solvent polyurethane synthetic leather is made of surface layer and foaming layer, and the surface layer and foaming layer use the poly- ammonia of two-component Ester resin is made, and dual-component polyurethane resin is made of component A and B component, surface layer, surface layer different with foaming layer component A It is identical with foaming layer B component.Wherein component A is polyhydroxy compound resin, and B component is isocyanate component.The A groups of surface layer Part is the A for not adding foaming agent1, foaming layer is to add the A of foaming agent with component A2.By A1, composition B through casting machine moment mix After be cast in release liners, 3~5min baking and curings at 110 DEG C, be made surface layer；By A2, B is poured into through casting machine and is applied to On surface layer polyurethane resin, with scraper drawout to 1-2mm thickness, sending to 1~2min of drying tunnel heating makes resin semi-solid preparation, prepares hair Alveolar layer, is then bonded non-woven fabrics base fabric, and 3~5min is cured into rear road baking oven.The Synthetic Leather obtained after curing carries out Release liners are peeled off, rolling and storage.
Performance test：GB T12704-1991 are pressed in penetrability test《Textile fabric vapor transfer rate method of testing-moisture-inhibiting agar diffusion method》 20 ± 2 DEG C of environment temperature, 65 ± 2% times tests of humidity.Permeability test presses GB 4689.2-1984 H.C Fedoroff leathers Permeability meter measures.The breathable moisture permeability test data of prepared uninanned platform leather is as shown in table 1.
The breathable moisture permeability test data of 1 solvent synthetic leather of table
As can be seen from Table 1, the methyl phenyl silicone modified isocyanate blocked by Amino End Group prepares pre- Aggressiveness, what its breathable moisture permeability of Synthetic Leather prepared using solventless method was prepared better than patent document CN106087451A Synthetic Leather；Since silicone segments have excellent compliance and gas permeability, with silicone molecules chain length Increase, the breathable moisture permeability of prepared Synthetic Leather are better.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments The present invention is described in detail, it will be understood by those of ordinary skill in the art that：It still can be to foregoing each implementation Technical solution described in example is modified, or carries out equivalent substitution to which part technical characteristic；And these modification or Replace, the essence of appropriate technical solution is departed from the spirit and scope of various embodiments of the present invention technical solution.

Claims (10)

  1. A kind of 1. organic-silicon-modified Isocyanate prepolymers body of no-solvent type use for synthetic leather, it is characterized in that containing following structure chemical combination Thing：
    Wherein, R is aryl or fat-based；A, b is natural number.
  2. 2. the organic-silicon-modified Isocyanate prepolymers body of no-solvent type use for synthetic leather according to claim 1, it is characterized in that, R Carbon number be 6~13.
  3. A kind of 3. side of the organic-silicon-modified Isocyanate prepolymers body of no-solvent type use for synthetic leather prepared described in claim 1 or 2 Method, comprises the following steps：
    (1) octamethylcy-clotetrasiloxane, tetramethyl tetraphenyl cyclotetrasiloxane and acidic catalyst are added into reactor, Ran Houjia Enter tetramethyldihydrogendisiloxane, at 60~80 DEG C, 4~6h of ring-opening polymerization, after reaction, cooling, reaction product is used For alkali neutralization to neutrality, washing, filtering, removing small molecule by-product, obtain the methyl phenyl silicone of end hydrogen-based end-blocking；
    (2) by the end hydrogen-based methyl phenyl silicone obtained in step (1) and allyl amine in H2PtCl6Reacted under catalyst, The methyl phenyl silicone of Amino End Group end-blocking is made；
    (3) product obtained in step (2) is carried out dehydrating, generation end group is then reacted with isocyanate-monomer again is The performed polymer of NCO.
  4. 4. according to the method described in claim 3, it is characterized in that the mode of step (1) removing small molecule by-product is using rotation Evaporimeter, revolving temperature are 100~130 DEG C.
  5. 5. according to the method described in claim 3, it is characterized in that step (2) reaction temperature is 50~60 DEG C, the reaction time for 3~ 5h；Used catalyst H2PtCl6Dosage is 10/1000000ths~the 30 of two kinds of reactant qualities.
  6. 6. according to the method described in claim 3, it is characterized in that step (1) described acidic catalyst is concentrated hydrochloric acid, the concentrated sulfuric acid, three One kind or composition in fluorine methanesulfonic acid or acid cation exchange resin；The dosage of acidic catalyst used is prestox ring The 1%~3% of tetrasiloxane and tetramethyl tetraphenyl cyclotetrasiloxane quality sum.
  7. 7. according to the method described in claim 3, it is characterized in that first hybrid reaction after acidic catalyst addition system in step (1) 30~40min, then adds tetramethyldihydrogendisiloxane.
  8. 8. the according to the method described in claim 3, it is characterized in that poly- silicon of aminomethyl phenyl that the end hydrogen-based of design blocks in step (1) The number-average molecular weight of oxygen alkane is 500~4000.
  9. 9. the according to the method described in claim 8, it is characterized in that poly- silicon of aminomethyl phenyl that the end hydrogen-based of design blocks in step (1) The number-average molecular weight of oxygen alkane is 1000~3000.
  10. 10. according to the method described in claim 3, the isocyanate-monomer is isophorone diisocyanate (IPDI), first Phenylene diisocyanate (TDI), methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), two methylene of benzene At least one of group diisocyanate (XDI) or Methylcyclohexyl diisocyanate (HTDI).
CN201711323525.9A 2017-11-30 2017-11-30 Organic silicon modified isocyanate prepolymer for solvent-free synthetic leather and preparation method thereof Active CN107936216B (en)

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CN112961307A (en) * 2021-02-09 2021-06-15 上海华峰新材料研发科技有限公司 Solvent-free polyurethane resin, impregnation slurry, preparation method and application thereof

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CN112961307A (en) * 2021-02-09 2021-06-15 上海华峰新材料研发科技有限公司 Solvent-free polyurethane resin, impregnation slurry, preparation method and application thereof

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