CN105985505A - Polyurethane composition capable of achieving free radical polymerization - Google Patents
Polyurethane composition capable of achieving free radical polymerization Download PDFInfo
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- CN105985505A CN105985505A CN201510092895.0A CN201510092895A CN105985505A CN 105985505 A CN105985505 A CN 105985505A CN 201510092895 A CN201510092895 A CN 201510092895A CN 105985505 A CN105985505 A CN 105985505A
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- isocyanate
- toluene
- tdi
- urethane composition
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Abstract
The invention relates to a polyurethane composition capable of achieving free radical polymerization. The polyurethane composition contains toluene diisocynate residues, has proper storage stability and operable time and high glass transition temperature, and can be prepared into various polyurethane composite materials with good heat resistance through various composite material forming technologies.
Description
Technical field
The present invention relates to the urethane composition of a kind of free redical polymerization, described urethane composition comprises
One or more toluene di-isocyanate(TDI) residues.Described polyether polyols with reduced unsaturation has suitable stable storing
Property and operable time and higher glass transition temperature, can be by various composite molding works
Skill is prepared as the various compound polyurethane materials with good heat resistance.
Background technology
Toluene di-isocyanate(TDI) (TDI) is the important source material preparing polyurethane material, and it generally passes through first
Phenylenediamine (TDA) and phosgene reaction prepare toluene di-isocyanate(TDI) crude product, then pass through distillation purifying
This crude product obtains required product.During the distillation of toluene di-isocyanate(TDI) crude product, can produce big
The high boiling point distillation leftover of amount, these residues have toxicity, and are difficult to process.
These distillation leftovers are generally processed by the method burned, and the poisonous fume that the method can produce needs
It is additionally carried out recycling.DE-A2942678 and CN102007096A discloses some and processes toluene
The method of diisocyanate distillation leftover, it is by, under acid or aqueous basic conditions, making these residual
Stay thing pyrohydrolysis to reclaim TDA.
Summary of the invention
The present invention provides the urethane composition of a kind of free redical polymerization, described urethane composition to comprise:
A) isocyanate component, described isocyanate component comprises:
A1) toluene di-isocyanate(TDI) residue, described toluene di-isocyanate(TDI) residue is selected from passing through phosgene
The distillation leftover of toluene di-isocyanate(TDI) prepared by method, wherein toluene di-isocyanate(TDI) residue NCO
Content is 5-40wt.%, and gross weight based on described toluene di-isocyanate(TDI) residue presses 100wt.%；
B) isocyanate-reactive component, described isocyanate-reactive component comprises:
B1) one or more have the compound of formula (I) structure
Wherein, R1Selected from hydrogen, methyl or ethyl；R2Selected from have 2-6 carbon atom alkylidene,
2,2-bis-(4-phenylene)-propane, Isosorbide-5-Nitrae-two (methylene) benzene, 1,3-bis-(methylene) benzene, 1,2-
Two (methylene) benzene；N is the integer selected from 1-6.
In one preferred embodiment of the present invention, described toluene di-isocyanate(TDI) residue is selected from by gas
The distillation leftover of toluene di-isocyanate(TDI) prepared by phase phosgenation.
In presently preferred embodiment, described isocyanate component A) also include:
A2) reactive diluent, described reactive diluent is selected from Styrene and its derivatives, acrylic acid
C1-C10Arrcostab, methacrylic acid C1-C10Arrcostab or a combination thereof, wherein said toluene diisocynate
Ester leftover a1) it is homogeneously dispersed in described reactive diluent.
In another preferred embodiment of the present invention, described b1) component is selected from: hydroxyethyl methacrylate second
Ester, Hydroxypropyl methacrylate, methacrylate, methacrylic acid hydroxy pentane ester, metering system
Acid the own ester of hydroxyl, 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, hy-droxybutyl, acrylic acid hydroxy pentane ester,
The own ester of acrylic acid hydroxyl or a combination thereof.
In the present invention also a preferred embodiment, described urethane composition also comprises: C) freely
Base reaction initiator.
Detailed description of the invention
The invention provides the urethane composition of a kind of free redical polymerization, described urethane composition bag
Contain:
A) isocyanate component, described isocyanate component comprises:
A1) toluene di-isocyanate(TDI) residue, described toluene di-isocyanate(TDI) residue is selected from passing through phosgene
The distillation leftover of toluene di-isocyanate(TDI) prepared by method, wherein toluene di-isocyanate(TDI) residue NCO
Content is 5-40wt.%, and gross weight based on described toluene di-isocyanate(TDI) residue presses 100wt.%；
B) isocyanate-reactive component, described isocyanate-reactive component comprises:
B1) one or more have the compound of formula (I) structure
Wherein, R1Selected from hydrogen, methyl or ethyl；R2Selected from have 2-6 carbon atom alkylidene,
2,2-bis-(4-phenylene)-propane, Isosorbide-5-Nitrae-two (methylene) benzene, 1,3-bis-(methylene) benzene, 1,2-
Two (methylene) benzene；N is the integer selected from 1-6.
The urethane composition of the free redical polymerization that the application provides has suitable storage stability
With operable time and higher glass transition temperature, various composite material process plannings can be passed through
It is prepared as the various compound polyurethane materials with good heat resistance.
As used in this application, term " urethane composition of free redical polymerization " refers to comprise and can send out
The urethane composition of the active ethylene linkage of raw Raolical polymerizable.As used in this application, term " is lived
Property ethylene linkage " refer to occur Raolical polymerizable carbon-carbon double bond.
In embodiments of the present invention, toluene di-isocyanate(TDI) residue is selected from the toluene prepared by phosgenation
The distillation leftover of diisocyanate.Those skilled in the art know phosgenation and prepare toluene di-isocyanate(TDI)
Technique, it is typically made up of 4 steps:
(1) toluene generates dinitrotoluene (DNT) (DNT) with nitric acid reaction；
(2) DNT and hydrogen react generation toluenediamine (TDA)；
(3) TDA generates toluene di-isocyanate(TDI) (TDI) with phosgene reaction；
(4) by distilation TDI.
The toluene di-isocyanate(TDI) residue that can be used for the present invention refers to obtain after distilation in the 4th step
The distillation leftover arrived, wherein toluene di-isocyanate(TDI) residue NCO content is 5-40wt.%, preferably
For 10-39wt.%, more preferably 25-38wt.%, based on described toluene di-isocyanate(TDI) residue total
Weight presses 100wt.%.
In the preferred embodiment of the invention, toluene di-isocyanate(TDI) residue is selected from by gas phase phosgenation
The distillation leftover of the toluene di-isocyanate(TDI) of preparation.Gas phase phosgenation method is characterised by above-mentioned steps (3)
In, TDA reacts through gas phase with phosgene, preferably at a temperature of 200-600 DEG C, prepares toluene diisocyanate
Acid esters.
Can be used for the isocyanate component A of the present invention) can also comprise: a2) reactive diluent.When with
When the present invention, " reactive diluent " refers to containing the active ethylene linkage that Raolical polymerizable can occur
Compound or compositions.In embodiments of the present invention, toluene di-isocyanate(TDI) residue can be equably
It is dispersed in reactive diluent.
In an embodiment of the present invention, reactive diluent is selected from Styrene and its derivatives, acrylic acid
C1-C10Arrcostab, methacrylic acid C1-C10Arrcostab or a combination thereof.Styrene derivative include but not
It is limited to halogen substituents and C1-C3Alkyl substituents.
Can be used for the isocyanate component A of the present invention) one or more organic polyisocyanic acid can also be comprised
Ester, it can be to become known for preparing any aliphatic series of polyurethane, alicyclic or aromatic isocyanate.Its
Example includes but not limited to: 2,2 '-, 2,4-and 4,4 '-methyl diphenylene diisocyanate；Haplotype hexichol
Dicyclohexylmethane diisocyanate and the mixture with more multi-ring methyl diphenylene diisocyanate homologue
(polymeric MDI)；Isophorone diisocyanate (IPDI) or its oligomer；Toluene di-isocyanate(TDI) (TDI),
Such as toluene diisocyanate isomers such as Toluene-2,4-diisocyanate, 4-or 2,6-diisocyanate, or its mixture；
Tetramethylene diisocyanate or its oligomer；Hexamethylene diisocyanate (HDI) or its oligomer；Naphthalene
Diisocyanate (NDI) or its mixture.
In an embodiment of the present invention, isocyanate-reactive component B) comprise one or more there is formula
(I) the compound b1 of structure)
Wherein, R1Selected from hydrogen, methyl or ethyl；R2Selected from the alkylidene with 2-6 carbon atom；n
For the integer selected from 1-6.
In the preferred embodiment of the invention, R2Selected from ethylidene, propylidene, butylidene, pentylidene,
1-methyl isophthalic acid, 2-ethylidene, 2-methyl isophthalic acid, 2-ethylidene, 1-ethyl-ethylene, 2-ethyl-1,2-Asia second
Base, 1-methyl isophthalic acid, 3-propylidene, 2-methyl isophthalic acid, 3-propylidene, 3-methyl isophthalic acid, 3-propylidene, 1-ethyl-1,3-
Propylidene, 2-ethyl-trimethylene, 3-ethyl-trimethylene, 1-methyl isophthalic acid, 4-butylidene, 2-methyl
-tetramethylene, 3-methyl isophthalic acid, 4-butylidene and 4-methyl isophthalic acid, 4-butylidene, 2,2-bis-(4-phenylene)-propane,
Isosorbide-5-Nitrae-dimethylene benzene, 1,3-dimethylene benzene, 1,2-dimethylene benzene.
In the preferred embodiment of the invention, described b1) component is selected from: hydroxyethyl methylacrylate, first
Base Hydroxypropyl acrylate, methacrylate, methacrylic acid hydroxy pentane ester, hydroxyethyl methacrylate are own
Ester, 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, hy-droxybutyl, acrylic acid hydroxy pentane ester, acrylic acid
The own ester of hydroxyl or a combination thereof.
Formula (I) compound can be prepared by method commonly used in the art, such as, can pass through (methyl) third
Olefin(e) acid acid anhydride or (methyl) acrylic acid, (methyl) acryloyl halide compound and HO-(R2O)n-H passes through ester
Changing reaction preparation, those skilled in the art know this preparation method, such as " urethane raw and auxiliary agent hands
Volume " (Liu Yijun, on April 1st, 2005 publish) chapter 3, " polyurethane elastomer " (Liu Houjun,
In August, 2012 publishes) explanation in chapter 2, the full content of the document is merged by reference
Enter herein.
In the preferred embodiment of the invention, the urethane composition of free redical polymerization can also comprise:
C) radical reaction initiator.Described radical reaction accelerator includes but not limited to peroxide, mistake
Sulfide, peroxycarbonates, peroxidating boric acid, azo-compound or other suitably can cause and contain
Double bond compound solidification radical reaction accelerator, the example include aoxidize isopropyl t-butyl carbonate,
Peroxidating-3,5,5-trimethylhexanoate, methyl ethyl ketone peroxide, isopropyl benzene hydroperoxide.Free radical
The content of reaction promoter is usually 0.1-8wt.%, and gross weight based on isocyanate-reactive component is pressed
100wt.% counts.
Can be used for isocyanate-reactive component B of the present invention) polyether polyol, polyethers carbon can also be comprised
Acid esters polyhydric alcohol, PEPA, PCDL, vegetable oil polyol or a combination thereof.
In an embodiment of the present invention, the urethane composition isocyanate index of free redical polymerization is
120-70, preferably 100-75, more preferably 99-85.
In embodiments of the present invention, the operable time of the urethane composition of free redical polymerization is
60-300 minute.As used in this application, term " operable time (pot-life) " refers to that polyurethane is opened
Originate raw Raolical polymerizable to its viscosity and reach the time of 600mPa s (25 DEG C).
It is public that the urethane composition of the free redical polymerization of the present invention possesses composite industry technical staff institute
The suitable storage stability known and operable time, the most also have higher glass transition temperature,
Can pass through well known to composite industry together with various reinforcing materials as composite matrix resin
Moulding process prepares compound polyurethane material by Raolical polymerizable solidification, and the polyurethane of preparation is combined
Material has higher glass transition temperature.
In the present invention hereinafter, the invention will be further described in conjunction with the embodiments.Disclosed in this invention
Specific embodiment and method, its description is illustrative and not restrictive.
Embodiment
Raw materials used in the embodiment of the present invention it is described as follows
Isocyanates A:TDI residue, NCO group content is 34.1%, and wherein monomer TDI accounts for institute
Stating the content in TDI residue is 50%；
Isocyanates B:TDI residue, NCO group content is 41.0%, and wherein monomer TDI accounts for institute
Stating the content in TDI residue is 75%；
Isocyanates C:NCO group content is 48.0%, and wherein monomer TDI accounts for described isocyanates group
Content in Fen is 100%；
Hydroxypropyl methacrylate (HPMA): can buy from Changzhou Hai Kelai company；
Norox MEKP-925H: radical reaction firming agent, can buy from Shuo Jin company；
Cobalt salt Accelerator NL-49P: radical reaction accelerator, can purchase from Akzo Nobel N.V.
:
Dabco T-12: organotin catalysts, can buy from Air Products company.
By isocyanates A (48 parts) and styrene (112 parts) mix homogeneously at embodiment 1:50 DEG C,
Add the T-12 of 0.1 part, be cooled to room temperature, again HPMA (56 parts) is progressively added drop-wise under stirring
State solution, after dripping, continue stirring reaction and within 5 hours, make the reaction of whole NCO group completely, then
The methyl hydroquinone adding above-mentioned total solution weight 0.1% i.e. can get polyurethane samples 1.
By isocyanates B (70 parts) and styrene (183 parts) mix homogeneously at embodiment 2:50 DEG C,
Add the T-12 of 0.1 part, be cooled to room temperature, again HPMA (100 parts) is progressively added drop-wise under stirring
Above-mentioned solution, after dripping, continues stirring reaction and within 5 hours, makes the reaction of whole NCO group completely,
The methyl hydroquinone adding above-mentioned total solution weight 0.1% i.e. can get polyurethane samples 2.
Embodiment 3: under room temperature, isocyanates C (60 parts) and styrene (170 parts) are mixed, add
The T-12 of 0.1 part, is progressively added drop-wise to above-mentioned solution by HPMA (100 parts) again under stirring, drips
After, continue stirring reaction and within 5 hours, make the reaction of whole NCO group completely, add above-mentioned solution total
The methyl hydroquinone of weight 0.1% i.e. can get polyurethane samples 3.
Storage stability is tested
The polyurethane samples prepared by embodiment 1-3, stores at normal temperatures and obvious viscosity does not occur in 40 days
Change and gelatin phenomenon.
Pot-life tests
Respectively take 100 parts of polyurethane samples prepared by embodiment 1-3, every kind of sample is pressed example weight again
Plus the Norox MEKP-925H of 2.0%, 1.0% cobalt salt Accelerator NL-49P.Above-mentioned sample
After each component of product resin stirs, measure the viscosity number of mixture system at set intervals.System
Being its Pot-life total time more than 600mPas from starting to viscosity, its result is shown in table 1.
Glass transition temperature (T
g
) test
Respectively take 100 parts of polyurethane samples prepared by embodiment 1-3, every kind of sample is pressed the weight of sample again
Plus the Norox MEKP-925H of 2.0%, the cobalt salt Accelerator NL-49P of 1.0%.Above-mentioned sample
After each component of resin stirs, standing 3 hours, 80 DEG C solidify 4 hours afterwards.Gained solidified sample takes
Sample DSC method tests respective glass transition temperature (Tg).
Table 1: the character of urethane composition
| Urethane composition | Pot-life(min.) | Tg(℃) |
| 1 | 122 | 151 |
| 2 | 147 | 140 |
| 3 | 185 | 136 |
From table 1 it follows that the present invention can urethane composition not only have suitable operable time
Between, and the resin matrix after solidifying has a good glass transition temperature, and remain containing TDI
The urethane composition that the Tg of the urethane composition of thing is prepared apparently higher than pure TDI.
Claims (5)
1. a urethane composition for free redical polymerization, described urethane composition comprises:
A) isocyanate component, described isocyanate component comprises:
A1) toluene di-isocyanate(TDI) residue, described toluene di-isocyanate(TDI) residue is selected from passing through phosgene
The distillation leftover of toluene di-isocyanate(TDI) prepared by method, wherein toluene di-isocyanate(TDI) residue NCO
Content is 5-40wt.%, and gross weight based on described toluene di-isocyanate(TDI) residue presses 100wt.%；
B) isocyanate-reactive component, described isocyanate-reactive component comprises:
B1) one or more have the compound of formula (I) structure
Wherein, R1Selected from hydrogen, methyl or ethyl；R2Selected from have 2-6 carbon atom alkylidene,
2,2-bis-(4-phenylene)-propane, Isosorbide-5-Nitrae-two (methylene) benzene, 1,3-bis-(methylene) benzene, 1,2-
Two (methylene) benzene；N is the integer selected from 1-6.
The urethane composition of free redical polymerization the most according to claim 1, wherein said toluene
Diisocyanate residue is selected from the distillation leftover of the toluene di-isocyanate(TDI) prepared by gas phase phosgenation.
The urethane composition of free redical polymerization the most according to claim 1 and 2, wherein said
Isocyanate component A) also include:
A2) reactive diluent, described reactive diluent is selected from Styrene and its derivatives, acrylic acid
C1-C10Arrcostab, methacrylic acid C1-C10Arrcostab or a combination thereof, wherein said toluene diisocynate
Ester leftover a1) it is homogeneously dispersed in described reactive diluent.
The urethane composition of free redical polymerization the most according to claim 1 and 2, wherein said
B1) component is selected from: hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, methacrylate,
The own ester of methacrylic acid hydroxy pentane ester, hydroxyethyl methacrylate, 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, third
Olefin(e) acid hydroxy butyl ester, acrylic acid hydroxy pentane ester, the own ester of acrylic acid hydroxyl or a combination thereof.
The urethane composition of free redical polymerization the most according to claim 1 and 2, wherein said
Urethane composition also comprises: C) radical reaction initiator.
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| CN201510092895.0A CN105985505A (en) | 2015-02-17 | 2015-02-17 | Polyurethane composition capable of achieving free radical polymerization |
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| CN201510092895.0A CN105985505A (en) | 2015-02-17 | 2015-02-17 | Polyurethane composition capable of achieving free radical polymerization |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022002784A1 (en) | 2020-06-30 | 2022-01-06 | Covestro Deutschland Ag | A polyurethane composition for preparing composites |
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|---|---|---|---|---|
| US3876728A (en) * | 1972-03-18 | 1975-04-08 | Hodogaya Chemical Co Ltd | Urethane resins from tolylene diisocyanate distillation residues active hydrogen containing compounds and vinyl monomers |
| US4506040A (en) * | 1983-08-01 | 1985-03-19 | Olin Corporation | Preparation of a stable dispersion from TDI residue and its use in the production of polyurethane compositions |
| EP0530302B1 (en) * | 1990-05-22 | 1995-11-15 | Dsm N.V. | Composition to be used in the resin injection moulding technique, containing low molecular weight compounds jointly forming a hybrid network |
| CN1405197A (en) * | 2002-10-31 | 2003-03-26 | 浙江大学 | Method for preparing optical polymer resin of high surface hardness |
| CN1505647A (en) * | 2001-04-12 | 2004-06-16 | Dsmip�Ʋ�����˾ | Lpa hybride |
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2015
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3876728A (en) * | 1972-03-18 | 1975-04-08 | Hodogaya Chemical Co Ltd | Urethane resins from tolylene diisocyanate distillation residues active hydrogen containing compounds and vinyl monomers |
| US4506040A (en) * | 1983-08-01 | 1985-03-19 | Olin Corporation | Preparation of a stable dispersion from TDI residue and its use in the production of polyurethane compositions |
| EP0530302B1 (en) * | 1990-05-22 | 1995-11-15 | Dsm N.V. | Composition to be used in the resin injection moulding technique, containing low molecular weight compounds jointly forming a hybrid network |
| CN1505647A (en) * | 2001-04-12 | 2004-06-16 | Dsmip�Ʋ�����˾ | Lpa hybride |
| CN1405197A (en) * | 2002-10-31 | 2003-03-26 | 浙江大学 | Method for preparing optical polymer resin of high surface hardness |
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| Title |
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| 丁彤等: "《中国化工产品大全》", 31 January 2005 * |
| 吴校彬等: "聚氨酯-丙烯酸酯的前端自由基聚合", 《化工学报》 * |
| 王鸿钧: "《发展循环经济实现节能减排》", 31 January 2008 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022002784A1 (en) | 2020-06-30 | 2022-01-06 | Covestro Deutschland Ag | A polyurethane composition for preparing composites |
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Effective date of registration: 20180828 Address after: Leverkusen, Germany Applicant after: BAYER MATERIALSCIENCE AG Address before: 201507 No. 82, Mu Hua Road, Shanghai chemical industry zone, Caojing, Shanghai Applicant before: A polymer (China) cosmos Co. Ltd. |
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Application publication date: 20161005 |