CN114507330B - Polyurethane composition - Google Patents

Polyurethane composition Download PDF

Info

Publication number
CN114507330B
CN114507330B CN202210013383.0A CN202210013383A CN114507330B CN 114507330 B CN114507330 B CN 114507330B CN 202210013383 A CN202210013383 A CN 202210013383A CN 114507330 B CN114507330 B CN 114507330B
Authority
CN
China
Prior art keywords
parts
acrylate
polyurethane composition
methyl
alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210013383.0A
Other languages
Chinese (zh)
Other versions
CN114507330A (en
Inventor
钟连兵
熊高虎
符罗坪
王恩东
彭豪
周百能
苟鹏飞
肖毅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan Dongshu New Material Co ltd
Original Assignee
Sichuan Dongshu New Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan Dongshu New Material Co ltd filed Critical Sichuan Dongshu New Material Co ltd
Priority to CN202210013383.0A priority Critical patent/CN114507330B/en
Publication of CN114507330A publication Critical patent/CN114507330A/en
Application granted granted Critical
Publication of CN114507330B publication Critical patent/CN114507330B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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
    • C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
    • 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
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • 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
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a polyurethane composition, and belongs to the technical field of polyurethane composite materials. The technical problem solved by the invention is to provide the polyurethane composition with small curing shrinkage and good mechanical property. The polyurethane composition of the invention comprises the following components: a. black material component: comprising a polyisocyanate and an initiator; b. white material components: including polyols and acrylic monomers; the polyalcohol comprises spiro-ring alcohol with a structure shown as a formula I. The invention adopts the spiro alcohol, overcomes the volume shrinkage of polyurethane resin during curing, improves the curing mechanical strength of the resin, and solves the problems of large curing shrinkage, easy deformation, accelerated aging, multiple defects and insufficient mechanical property of the existing resin system. The polyurethane obtained by curing the polyurethane composition has the advantages of low volume shrinkage as low as 0 and good mechanical property, can be used for vacuum infusion process or pultrusion process molding, and has better appearance and better mechanical property.

Description

Polyurethane composition
Technical Field
The invention relates to a polyurethane composition, and belongs to the technical field of polyurethane composite materials.
Background
Polyurethane (PU), which is a polymer compound and contains a repeating-HNCOO-group in its main chain, is generally obtained by stepwise addition polymerization of a polyisocyanate, a polyol polymer, an aromatic diamine, and the like. The polyurethane molecule may contain, in addition to the urethane, ether, ester, urea, biuret, allophanate, etc. By changing the types and the compositions of the raw materials, the shape and the performance of the polyurethane resin product can be greatly changed, and a soft to hard final product can be obtained. Polyurethane resin has the outstanding advantages of low cost, excellent mechanical properties, good weather resistance and the like, and in recent years, polyurethane-based composite materials are increasingly studied.
The kesiju corporation publication reports a series of methods and patents for polyurethane preparation of composite materials, such as patent CN111748073A, CN105778005A, CN104974502A, CN105199075a, etc. The technology of the patent mainly uses an unsaturated double bond-based reactive diluent as a reactant (such as methyl (methyl) acrylate, (methyl) hydroxyl acrylate and the like), and the prepared casting body and composite material products have the defects of large curing shrinkage, poor mechanical properties and the like, so that the application of the reactive diluent in various fields of wind power blades, yacht bodies and automobile engine covers is affected.
Disclosure of Invention
Aiming at the defect of large curing shrinkage of polyurethane, the invention solves the technical problem of providing a polyurethane composition with small curing shrinkage and good mechanical property.
The polyurethane composition of the invention comprises the following components:
a. black material component: comprising a polyisocyanate and an initiator;
b. white material components: including polyols and acrylic monomers; the polyalcohol comprises spiro alcohol;
wherein the structure of the spiro alcohol is shown as a formula I:
the structure of the acrylic monomer is shown as a formula II:
in the formula II, R 1 Is hydrogen or methyl, R 2 Is alkyl, cycloalkyl or hydroxyalkyl.
In one embodiment of the present invention, the acrylic monomer is at least one of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
In a preferred embodiment, the acrylic monomers are methyl (meth) acrylate and hydroxypropyl (meth) acrylate.
In a more preferred embodiment, the weight ratio of methyl (meth) acrylate to hydroxypropyl (meth) acrylate is from 1:8 to 15.
In one embodiment, the weight ratio of methyl (meth) acrylate to hydroxypropyl (meth) acrylate is 1:11.
Further, the polyol may further comprise a polyether polyol or a polyester polyol.
In one embodiment of the invention, the spiro alcohol comprises 10 to 15 weight percent of the polyol.
In a preferred embodiment, the spirocyclic alcohol comprises 13% by weight of the polyol.
In one embodiment of the present invention, the weight ratio of polyol to acrylic monomer is 1:1-3.
In a preferred embodiment, the weight ratio of polyol to acrylate monomer is 1:1.5.
In one embodiment of the invention, the white material component further comprises an auxiliary agent, wherein the auxiliary agent is at least one of a free radical polymerization inhibitor, a chain extender, a water scavenger, a surfactant, an accelerator and a gel catalyst.
In one embodiment of the invention, the weight ratio of the white material component to the black material component is 100:40-130.
In a preferred embodiment, the weight ratio of white and black components is 100:85.
As a preferred scheme, the white material component consists of the following components in parts by weight: 40-60 parts of methyl methacrylate, 400-650 parts of hydroxypropyl methacrylate, 150-250 parts of 3-functional polyether polyol, 100-200 parts of 2-functional polyol, 40-60 parts of spirocyclic alcohol, 0.01-0.5 part of free radical polymerization inhibitor, 1-10 parts of chain extender, 0.1-1 part of water scavenger, 1-5 parts of surfactant, 0.5-2 parts of cobalt naphthenate and 0.01-0.2 part of gel catalyst.
In a preferred embodiment, the white material component consists of the following components in parts by weight: 50 parts of methyl methacrylate, 550 parts of hydroxypropyl methacrylate, 200 parts of 3-functional polyether polyol, 148 parts of 2-functional polyol, 52 parts of spirocyclic alcohol, 0.1 part of free radical polymerization inhibitor, 5 parts of chain extender, 0.5 part of water scavenger, 2 parts of surfactant, 1 part of cobalt naphthenate and 0.1 part of gel catalyst.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the spiro alcohol, overcomes the volume shrinkage of polyurethane resin during curing, improves the curing mechanical strength of the resin, and solves the problems of large curing shrinkage, easy deformation, accelerated aging, multiple defects and insufficient mechanical property of the existing resin system. The polyurethane obtained by curing the polyurethane composition has the advantages of low volume shrinkage as low as 0 and good mechanical property, can be used for vacuum infusion process or pultrusion process molding, and has better appearance and better mechanical property.
Detailed Description
The polyurethane composition of the invention comprises the following components:
a. black material component: comprising a polyisocyanate and an initiator;
b. white material components: including polyols and acrylic monomers; the polyalcohol comprises spiro alcohol;
wherein the structure of the spiro alcohol is shown as a formula I:
the structure of the acrylic monomer is shown as a formula II:
in the formula II, R 1 Is hydrogen or methyl, R 2 Is alkyl, cycloalkyl or hydroxyalkyl.
Generally, volume expansion can be generated in the polyurethane polymerization process, and the invention adopts spiro alcohol, thereby overcoming the volume shrinkage of polyurethane resin during curing, improving the curing mechanical strength of the resin, and solving the problems of large curing shrinkage, easy deformation, accelerated aging, multiple defects and insufficient mechanical property of the existing resin system. The polyurethane obtained by curing the polyurethane composition has the advantages of low volume shrinkage as low as 0 and good mechanical property, can be used for vacuum infusion process or pultrusion process molding, and has better appearance and better mechanical property.
Wherein, the component a is a black material component which comprises polyisocyanate and an initiator.
The polyisocyanate of the present invention is a generic term for various esters containing 2 or more isocyanate groups. Polyisocyanates commonly used in the art are suitable for use in the present invention. In some embodiments of the present invention, the polyisocyanate includes, but is not limited to, toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), lysine Diisocyanate (LDI), 1, 5-Naphthalene Diisocyanate (NDI), terephthal-diisocyanate (PPDI), terephthal-methylene diisocyanate (XDI), and the like, as well as polymers of these isocyanates or combinations thereof.
The initiator mainly initiates double bonds in the white material component to generate free radical reaction. Free radical initiators commonly used in the art are suitable for use in the present invention and include, but are not limited to, benzoyl peroxide, lauroyl peroxide, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyvalerate, methyl ethyl ketone peroxide, cyclohexanone peroxide, and the like. The free radical initiator is used in amounts conventional in the art.
The component b is a white material component which comprises polyalcohol containing spiro alcohol and acrylic ester monomer.
The spirocyclic alcohol is an active monomer with a spiro structure and hydroxyl, and the addition of the spirocyclic alcohol in the polyurethane composition not only overcomes the defects of large curing shrinkage of the existing unsaturated resin modified polyurethane system, but also further improves the curing mechanical strength of the resin. The structure of the spirocyclic alcohol is shown as a formula I:
the spirocyclic alcohol can be commercially available or self-made. In one embodiment of the invention, the spirocyclic alcohol is prepared by the following method:
the spirocyclic alcohol is synthesized with tetraethyl orthocarbonate by taking trimethylol propane as a starting raw material and hydrochloric acid, acetic acid, p-toluenesulfonic acid, sulfuric acid or nitric acid as a catalyst, and the synthetic route is as follows:
in one embodiment of the present invention, the acrylic monomer is at least one of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
(meth) acrylic acid … … "as used herein refers to acrylic acid … … or methacrylic acid … …. For example, hydroxyethyl (meth) acrylate is hydroxyethyl acrylate or hydroxyethyl methacrylate, methyl (meth) acrylate is methyl acrylate or methyl methacrylate, and ethyl (meth) acrylate is ethyl acrylate or ethyl methacrylate.
In a preferred embodiment, the acrylic monomers are methyl (meth) acrylate and hydroxypropyl (meth) acrylate.
In a more preferred embodiment, the weight ratio of methyl (meth) acrylate to hydroxypropyl (meth) acrylate is from 1:8 to 15.
In one embodiment, the weight ratio of methyl (meth) acrylate to hydroxypropyl (meth) acrylate is 1:11.
Further, the polyol may further comprise a polyether polyol or a polyester polyol.
In one embodiment of the invention, the spiro alcohol comprises 10 to 15 weight percent of the polyol.
In a preferred embodiment, the spirocyclic alcohol comprises 13% by weight of the polyol.
In one embodiment of the present invention, the weight ratio of polyol to acrylic monomer is 1:1-3.
In a preferred embodiment, the weight ratio of polyol to acrylate monomer is 1:1.5.
In one embodiment of the invention, the white material component further comprises an auxiliary agent, wherein the auxiliary agent is at least one of a free radical polymerization inhibitor, a chain extender, a water scavenger, a surfactant, an accelerator and a gel catalyst.
In one embodiment of the invention, the free radical polymerization inhibitor is methyl hydroquinone, the chain extender is dipropylene glycol, the water scavenger is triethyl orthoformate, the surfactant is silicone oil B8870, the accelerator is cobalt naphthenate, and the gel catalyst is polyurethane organic bismuth catalyst BICAT8.
In one embodiment of the invention, the weight ratio of the white material component to the black material component is 100:40-130.
In a preferred embodiment, the weight ratio of white and black components is 100:85.
As a preferred scheme, the white material component consists of the following components in parts by weight: 40-60 parts of methyl methacrylate, 400-650 parts of hydroxypropyl methacrylate, 150-250 parts of 3-functional polyether polyol, 100-200 parts of 2-functional polyol, 40-60 parts of spirocyclic alcohol, 0.01-0.5 part of free radical polymerization inhibitor, 1-10 parts of chain extender, 0.1-1 part of water scavenger, 1-5 parts of surfactant, 0.5-2 parts of cobalt naphthenate and 0.01-0.2 part of gel catalyst.
In a preferred embodiment, the white material component consists of the following components in parts by weight: 50 parts of methyl methacrylate, 550 parts of hydroxypropyl methacrylate, 200 parts of 3-functional polyether polyol, 148 parts of 2-functional polyol, 52 parts of spirocyclic alcohol, 0.1 part of free radical polymerization inhibitor, 5 parts of chain extender, 0.5 part of water scavenger, 2 parts of surfactant, 1 part of cobalt naphthenate and 0.1 part of gel catalyst.
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto.
Examples
The formulation of the polyurethane composition of the present invention is shown in Table 1.
TABLE 1
Wherein PM200 is polymeric MDI having a functionality of 2.7 and an NCO content of 30.75%, available from Wanhua chemical polyurethane company.
HPMA is hydroxypropyl methacrylate.
DMT450 is a trimethylolpropane starter dose of 3-functional polyether polyol, molecular weight 450, available from Shandong Bode Federal chemical industry Co.
DL400 is a propylene glycol-initiated 2-functional polyether polyol having a molecular weight of 400 available from Shandong blue Star Dongda Co.
MMA is methyl methacrylate.
The spirocyclic alcohol was self-made and prepared as described in example 3 with reference to CN 112812124A.
Performance test:
1. mechanical properties of casting machine
According to the weight ratio of the black material to the white material of 100 parts, 85 parts of the black material are mixed to prepare a casting body, the preparation condition of the casting body is room temperature condition, the temperature is 20-25 ℃, the humidity is 50-65%, and the curing condition is that: the two components are mixed and defoamed, then are led into a glass interlayer, are kept stand for 24 hours, are heated to 70 ℃ and are cured for 4 hours. And (5) taking out, cutting and polishing the sample into standard-size sample bars, and measuring the mechanical properties according to the sample bars. The results are shown in Table 2.
TABLE 2
Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2
Tensile Strength/MPa 91.5 93.5 93.8 75.2 74.5
Tensile modulus/Gpa 3.62 3.71 3.82 3.09 3.25
Elongation at break/% 7.28 8.52 6.43 5.63 5.12
Flexural Strength/MPa 142 148 140 118 108
Flexural modulus/Gpa 3.88 3.85 3.77 3.28 3.06
Volume shrinkage% 0 0.24 0.13 11.5 -3.2
Therefore, the casting body prepared by the invention completely overcomes the shrinkage defect after solidification, and has higher mechanical strength and better comprehensive performance.
2. FRP (fiber reinforced Plastic) for vacuum pouring process
The two components are uniformly mixed according to the proportion of 100:85 of white materials to black materials, defoamed, glass fiber type of Zhejiang Hengshi UD1200, 4 layers are paved, after being uniformly mixed by vacuum defoamation, FRP is poured, and then the performance is measured, and the result is shown in Table 3.
TABLE 3 Table 3
3. Pultrusion process FRP
Using a pultrusion process, glass fiber raw yarn was TMII type of International composite materials for Daqing, the number of yarns was 406 yarns, the temperature in the three regions was 100℃in the first region, 160℃in the second region, 185℃in the third region, and the pultrusion speed was 1m/min, FRP was produced, and then the properties thereof were measured, and the results are shown in Table 4.
TABLE 4 Table 4
It can be seen that the product of the invention has better product appearance and better mechanical property under the condition of the same glass fiber content no matter vacuum pouring or pultrusion.

Claims (9)

1. Polyurethane composition, characterized in that it comprises the following components:
a. black material component: comprising a polyisocyanate and an initiator;
b. white material components: including polyols and acrylic monomers; the polyalcohol comprises spiro alcohol;
wherein the structure of the spiro alcohol is shown as a formula I:
i
The spirocyclic alcohol accounts for 10-15% of the polyol by weight; the acrylic monomer is methyl (methyl) acrylate and hydroxypropyl (methyl) acrylate; the weight ratio of the methyl (methyl) acrylate to the hydroxypropyl (methyl) acrylate is 1:8-15; the weight ratio of the polyalcohol to the acrylic monomer is 1:1-3; the weight ratio of the white material component to the black material component is 100:40-130.
2. The polyurethane composition of claim 1, wherein: the weight ratio of methyl (meth) acrylate to hydroxypropyl (meth) acrylate was 1:11.
3. The polyurethane composition of claim 1, wherein: the polyols also include polyether polyols or polyester polyols.
4. The polyurethane composition of claim 1, wherein: the weight percentage of the spirocyclic alcohol in the polyol is 13%.
5. The polyurethane composition of claim 1, wherein: the weight ratio of the polyol to the acrylic monomer is 1:1.5.
6. The polyurethane composition of claim 1, wherein: the white material component also comprises an auxiliary agent, wherein the auxiliary agent is at least one of a free radical polymerization inhibitor, a chain extender, a water scavenger, a surfactant, an accelerator and a gel catalyst.
7. The polyurethane composition of claim 1, wherein: the weight ratio of the white material component to the black material component is 100:85.
8. The polyurethane composition of claim 1, wherein: the white material comprises the following components in parts by weight: 40-60 parts of methyl methacrylate, 400-650 parts of hydroxypropyl methacrylate, 150-250 parts of 3-functional polyether polyol, 100-200 parts of 2-functional polyol, 40-60 parts of spirocyclic alcohol, 0.01-0.5 part of free radical polymerization inhibitor, 1-10 parts of chain extender, 0.1-1 part of water scavenger, 1-5 parts of surfactant, 0.5-2 parts of cobalt naphthenate and 0.01-0.2 part of gel catalyst.
9. The polyurethane composition of claim 1, wherein: the white material comprises the following components in parts by weight: 50 parts of methyl methacrylate, 550 parts of hydroxypropyl methacrylate, 200 parts of 3-functional polyether polyol, 148 parts of 2-functional polyol, 52 parts of spirocyclic alcohol, 0.1 part of free radical polymerization inhibitor, 5 parts of chain extender, 0.5 part of water scavenger, 2 parts of surfactant, 1 part of cobalt naphthenate and 0.1 part of gel catalyst.
CN202210013383.0A 2022-01-06 2022-01-06 Polyurethane composition Active CN114507330B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210013383.0A CN114507330B (en) 2022-01-06 2022-01-06 Polyurethane composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210013383.0A CN114507330B (en) 2022-01-06 2022-01-06 Polyurethane composition

Publications (2)

Publication Number Publication Date
CN114507330A CN114507330A (en) 2022-05-17
CN114507330B true CN114507330B (en) 2024-02-23

Family

ID=81549632

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210013383.0A Active CN114507330B (en) 2022-01-06 2022-01-06 Polyurethane composition

Country Status (1)

Country Link
CN (1) CN114507330B (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4338240A (en) * 1980-07-16 1982-07-06 Toagoesi Chemical Industry Co., Ltd. Curable material and process for production thereof
JPH05125141A (en) * 1990-07-13 1993-05-21 Toyo Tire & Rubber Co Ltd Method for producing rigid polyurethane foam
US5494990A (en) * 1994-04-04 1996-02-27 Hodogaya Chemical Co., Ltd. Thermoplastic polyurethane resin having broad rubbery-state region and process for producing the same
WO2002057339A1 (en) * 2001-01-12 2002-07-25 E.I. Dupont De Nemours And Company Polymeric crosslinkable compositions containing spiroorthocarbonates
CN102796111A (en) * 2012-09-10 2012-11-28 贵州大学 Carboxylate (sulfonate) compounds with oxoaza-spiro-amido group, and preparation method and application thereof
CN102911337A (en) * 2012-07-02 2013-02-06 北京化工大学 Polyurethane acrylate oligomer and preparation method thereof
CN106674476A (en) * 2017-01-22 2017-05-17 江苏旭泽技术有限公司 Low-shrinkage UV curing PUA resin, as well as preparation method and application thereof to preparation of hot bending membrane
TW201922831A (en) * 2017-10-27 2019-06-16 日商迪愛生股份有限公司 Urethane resin composition, coating film and synthetic leather
CN112048051A (en) * 2019-06-05 2020-12-08 万华化学（北京）有限公司 Polyurethane acrylate resin and preparation method thereof
CN112812124A (en) * 2020-12-31 2021-05-18 深圳市聚诚新材科技有限公司 Novel spiro-expansion monomer containing unsaturated bond and ester group and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4338240A (en) * 1980-07-16 1982-07-06 Toagoesi Chemical Industry Co., Ltd. Curable material and process for production thereof
JPH05125141A (en) * 1990-07-13 1993-05-21 Toyo Tire & Rubber Co Ltd Method for producing rigid polyurethane foam
US5494990A (en) * 1994-04-04 1996-02-27 Hodogaya Chemical Co., Ltd. Thermoplastic polyurethane resin having broad rubbery-state region and process for producing the same
WO2002057339A1 (en) * 2001-01-12 2002-07-25 E.I. Dupont De Nemours And Company Polymeric crosslinkable compositions containing spiroorthocarbonates
CN102911337A (en) * 2012-07-02 2013-02-06 北京化工大学 Polyurethane acrylate oligomer and preparation method thereof
CN102796111A (en) * 2012-09-10 2012-11-28 贵州大学 Carboxylate (sulfonate) compounds with oxoaza-spiro-amido group, and preparation method and application thereof
CN106674476A (en) * 2017-01-22 2017-05-17 江苏旭泽技术有限公司 Low-shrinkage UV curing PUA resin, as well as preparation method and application thereof to preparation of hot bending membrane
TW201922831A (en) * 2017-10-27 2019-06-16 日商迪愛生股份有限公司 Urethane resin composition, coating film and synthetic leather
CN112048051A (en) * 2019-06-05 2020-12-08 万华化学（北京）有限公司 Polyurethane acrylate resin and preparation method thereof
CN112812124A (en) * 2020-12-31 2021-05-18 深圳市聚诚新材科技有限公司 Novel spiro-expansion monomer containing unsaturated bond and ester group and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Ring-Opening Polymerization with Expansion in Volume;WILLIAM J. BAILEY;《ACS Symposium Series》(第59期);第38-59页 *

Also Published As

Publication number Publication date
CN114507330A (en) 2022-05-17

Similar Documents

Publication Publication Date Title
US9181380B2 (en) Thermosetting resin composition
CN105778005B (en) Free-radically polymerizable polyurethane composition
CN104045806B (en) Polyurethane composition for preparing polyurethane composite material
WO2021139135A1 (en) Isocyanate prepolymer for polyurethane-fiber composite materials, preparation method therefor and use thereof
CN111019089B (en) Polyurethane composite material and preparation method thereof
EP0051476A2 (en) Modified polyurethane liquid polymer compositions and their preparation
EP0052958A2 (en) Modified polyurethane liquid polymer compositions and their preparation
AU2019225884B2 (en) Polyurethane-based polymer material having excellent resistance to heat distortion and elongation at tear
CN114507330B (en) Polyurethane composition
JPH06157707A (en) Crosslinkable polyester/isocyanate composition and its preparation and use
US4544730A (en) Modified polyurethane liquid polymer compositions
CN114369226B (en) Lightweight polyurethane elastomer and manufacturing method and application thereof
US4522969A (en) Modified polyurethane liquid polymer compositions
US20220184901A1 (en) Method for preparing a pultruded polyurethane composite
JP3093262B2 (en) Composition for use in a resin injection molding method, comprising a low molecular weight compound forming a hybrid network
CN114479001B (en) Two-component polyurethane compositions
CN114437310B (en) Modified polyurethane composition and application thereof
EP3733729A1 (en) Method for preparing a pultruded polyurethane composite
JP3073070B2 (en) Method for producing in-mold cured product having high glass transition temperature and in-mold cured product having high glass transition temperature obtained by the production method
US4552917A (en) Modified polyurethane liquid polymer compositions
KR102647123B1 (en) Urethane modified acrylic resin composition and the method of preparing the same
US4463158A (en) Modified polyurethane liquid polymer compositions
US4533717A (en) Modified polyurethane liquid polymer compositions
US4552943A (en) Modified polyurethane liquid polymer compositions
EP4223826A1 (en) Isocyanate composition and use thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant