CN107880249A - A kind of polyurethane curing agent and preparation method thereof - Google Patents
A kind of polyurethane curing agent and preparation method thereof Download PDFInfo
- Publication number
- CN107880249A CN107880249A CN201711189238.3A CN201711189238A CN107880249A CN 107880249 A CN107880249 A CN 107880249A CN 201711189238 A CN201711189238 A CN 201711189238A CN 107880249 A CN107880249 A CN 107880249A
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- parts
- curing agent
- tdi
- polyurethane curing
- mdi
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Classifications
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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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
-
- 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
- C08G18/6677—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 having at least three hydroxy groups
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- 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 discloses a kind of polyurethane curing agent, is made up of the raw material of following parts by weight：50 70 parts of methyl diphenylene diisocyanate (MDI), 10 12 parts of trimethylolpropane (TMP), 25 parts of PPG, 8 12 parts of butyl acetate, 10 15 parts of dimethylbenzene, 13 parts of levelling agent, 13 parts of defoamer.Methyl diphenylene diisocyanate (MDI) has preferable pliability and shorter construction period than toluene di-isocyanate(TDI) (TDI), its combination property is close to TDI TMP addition products, and production cost is greatly lowered, smell, small toxicity, be advantageous to worker's health, be a kind of extremely wide curing agent of development prospect.
Description
Technical field
The invention belongs to paint field, and in particular to a kind of polyurethane curing agent and preparation method thereof.
Background technology
Environment-friendly is the development trend of coating, with the polyurethane curing agent of toluene di-isocyanate(TDI) (TDI) synthesis to people
Class and larger to the harmfulness of environment, it would be highly desirable to seek it is a kind of substitute composition, dropped on the premise of equal above combination property is realized
The toxicity of oligourethane curing agent.
The content of the invention
It is an object of the present invention to overcome above-mentioned prior art defect, there is provided a kind of polyurethane curing agent and its preparation
Method, feature are to instead of toluene di-isocyanate(TDI) (TDI) with methyl diphenylene diisocyanate (MDI).
Technical scheme is used by the present invention solves above-mentioned technical problem：
A kind of polyurethane curing agent, it is made up of the raw material of following parts by weight：Methyl diphenylene diisocyanate (MDI)
50-70 parts, trimethylolpropane (TMP) 10-12 parts, PPG 2-5 parts, butyl acetate 8-12 parts, dimethylbenzene 10-15
Part, levelling agent 1-3 parts, defoamer 1-3 parts.
Preferably, it is made up of the raw material of following parts by weight：63 parts of methyl diphenylene diisocyanate (MDI), three hydroxyl first
11 parts of base propane (TMP), 3.5 parts of PPG, 10 parts of butyl acetate, 12 parts of dimethylbenzene, 2 parts of levelling agent, 2 parts of defoamer.
A kind of method for preparing described polyurethane curing agent, comprises the following steps：
(1) to PPG and trimethylolpropane (TMP) reflux dewatering under 130~140 DEG C of high temperature；
(2) less than 80 DEG C are cooled to, then puts into dimethylbenzene, methyl diphenylene diisocyanate (MDI) monomer is melted
Melt polymerisation, in 65~80 DEG C of insulations, react 1-3h；
(3) sample, with di-n-butylamine method detection architecture-NCO content, cool after reaching requirement, add acetic acid fourth
Ester, levelling agent and defoamer, filtering and discharging after disperseing.
Synthesis and curing mechanism are as follows：
Polyurethane curing agent with polyisocyanate-based (- NCO) for base-material, it is anti-with polyisocyanates using PPG
The prepolymer that end group contains NCO should be made.When its moisture solidification, steam in air is with molecular conformation to coating
Middle infiltration, and-NCO reaction generation amine, and then cause to be crosslinked between prepolymer molecule, coating with-NCO reactions generation urea again
Final curing turns into the film of tough and hard wear resistant.When it is with colored paint component compounding use containing-OH ,-OH can exist with-NCO
Reacted under low temperature.
The present invention compared with prior art, has the advantages that：
Methyl diphenylene diisocyanate (MDI) has preferable pliability and shorter than toluene di-isocyanate(TDI) (TDI)
Construction period, its combination property is close to TDI-TMP addition products, and production cost is greatly lowered, and smell, small toxicity, has
It is a kind of extremely wide curing agent of development prospect beneficial to worker's health.The combination property of the polyurethane is good, illustrate with
It is feasible that MDI, which replaces TDI synthesis of polyurethane curing agent,.When polyurethane curing agent is moisture solidification, the envelope of floor coatings can be made
Priming paint is closed, there is excellent permeance property, the pore of concrete structure can be effectively sealing off, improves floor coatings and concrete
Basic adhesive property.When as Lacquer finish finish paint in use, with good levelability, wearability and glossiness；It is environment-friendly
It is the development trend of coating, MDI is much smaller than TDI coating to the mankind and to the harmfulness of environment.Colored paint group with hydroxyl simultaneously
Divide compounding use, color is homogeneous, plentiful attractive in appearance, available for common flat painting and mortar terrace.So used with MDI substitution TDI synthesis
There is larger development prospect in the polyurethane curing agent of floor coatings.
Embodiment
The present invention is further illustrated below by embodiment, following examples are the specific embodiment party of the present invention
Formula, but embodiments of the present invention are not limited by following embodiments.
Embodiment 1
A kind of polyurethane curing agent, it is made up of the raw material of following parts by weight：Methyl diphenylene diisocyanate (MDI) 63
Part, 11 parts of trimethylolpropane (TMP), 3.5 parts of PPG, 10 parts of butyl acetate, 12 parts of dimethylbenzene, 2 parts of levelling agent, disappear
2 parts of infusion.
A kind of method for preparing described polyurethane curing agent, comprises the following steps：
(1) to PPG and trimethylolpropane (TMP) reflux dewatering under 135 DEG C of high temperature；
(2) 70 DEG C are cooled to, then puts into dimethylbenzene, methyl diphenylene diisocyanate (MDI) monomer carries out melting and gathered
Reaction is closed, in 70 DEG C of insulations, reacts 2h；
(3) sample, with di-n-butylamine method detection architecture-NCO content, cool after reaching requirement, add acetic acid fourth
Ester, levelling agent and defoamer, filtering and discharging after disperseing.
Embodiment 2
A kind of polyurethane curing agent, it is made up of the raw material of following parts by weight：Methyl diphenylene diisocyanate (MDI) 50
Part, 10 parts of trimethylolpropane (TMP), 2 parts of PPG, 8 parts of butyl acetate, 10 parts of dimethylbenzene, 1 part of levelling agent, defoaming
1 part of agent.
A kind of method for preparing described polyurethane curing agent, comprises the following steps：
(1) to PPG and trimethylolpropane (TMP) reflux dewatering under 130 DEG C of high temperature；
(2) 60 DEG C are cooled to, then puts into dimethylbenzene, methyl diphenylene diisocyanate (MDI) monomer carries out melting and gathered
Reaction is closed, in 65 DEG C of insulations, reacts 1h；
(3) sample, with di-n-butylamine method detection architecture-NCO content, cool after reaching requirement, add acetic acid fourth
Ester, levelling agent and defoamer, filtering and discharging after disperseing.
Embodiment 3
A kind of polyurethane curing agent, it is made up of the raw material of following parts by weight：Methyl diphenylene diisocyanate (MDI) 70
Part, 12 parts of trimethylolpropane (TMP), 5 parts of PPG, 12 parts of butyl acetate, 15 parts of dimethylbenzene, 3 parts of levelling agent, defoaming
3 parts of agent.
A kind of method for preparing described polyurethane curing agent, comprises the following steps：
(1) to PPG and trimethylolpropane (TMP) reflux dewatering under 140 DEG C of high temperature；
(2) 80 DEG C are cooled to, then puts into dimethylbenzene, methyl diphenylene diisocyanate (MDI) monomer carries out melting and gathered
Reaction is closed, in 80 DEG C of insulations, reacts 3h；
(3) sample, with di-n-butylamine method detection architecture-NCO content, cool after reaching requirement, add acetic acid fourth
Ester, levelling agent and defoamer, filtering and discharging after disperseing.
Performance requirement：
| Free TDI | GB/T 18446-2001 |
| Surface drying time | GB/T 1728-1979(1989) |
| Pencil hardness | GB/T 6739-1996 |
| Impact resistance | GB/T 1732-1993 |
| Adhesive force | GB/T 9286-1998 |
| Pliability | GB/T 1731-1993 |
| Wearability | ISO 7784-2:1997 |
| Storage stability | Sample is placed in 60 DEG C of baking oven storages, observes the storage stability of each sample |
Free TDI content determines：
Single component moisture solidification polyurethane performed polymer is respectively synthesized instead of part or all of TDI with MDI, by equivalent generation
Replacing, MDI synthesizes performed polymer sample instead of 1/4,1/2,3/4 and 100% TDI respectively, respectively with 2,3,4,5 marks, and with
The performed polymer (being labeled as 1) of pure TDI synthesis compares.
The test (Gu it is 40% to contain) of free TDI has been carried out to performed polymer sample 1,2,3,4,5, has measured the trip of each sample
It is respectively from TDI contents w (%)：2.7、1.8、1.2、0.5、0.
Result of the test shows, the performed polymer of TDI synthesis is replaced with MDI, significantly reduces free TDI content.Because MDI
Molecular weight it is larger, steam forces down：At 25 DEG C, TDI vapour pressure is 3.3Pa, and MDI vapour pressure is 0.012Pa, MDI's
Vapour pressure is only about the 4 ‰ of TDI vapour pressures.So the product volatility synthesized with MDI is small, without TDI intense irritation gas
Taste, environmental pollution is small, relatively small to human toxicity, is advantageous to industry security protection and worker's health.
It should be understood that these embodiments are only illustrative of the invention and is not intended to limit the scope of the invention.Reading this
Invent lecture content after, those skilled in the art the present invention can be made with any same or similar means it is various conversion or
Modification, these equivalent form of values are equally fallen under the scope of the present invention.
Claims (3)
1. a kind of polyurethane curing agent, it is characterised in that be made up of the raw material of following parts by weight：Diphenylmethane diisocyanate
Ester 50-70 parts, trimethylolpropane 10-12 parts, PPG 2-5 parts, butyl acetate 8-12 parts, dimethylbenzene 10-15 parts, stream
Flat agent 1-3 parts, defoamer 1-3 parts.
2. polyurethane curing agent according to claim 1, it is characterised in that be made up of the raw material of following parts by weight：Hexichol
63 parts of dicyclohexylmethane diisocyanate, 11 parts of trimethylolpropane, 3.5 parts of PPG, 10 parts of butyl acetate, dimethylbenzene 12
Part, 2 parts of levelling agent, 2 parts of defoamer.
A kind of 3. method for preparing the polyurethane curing agent described in claim 1 or 2, it is characterised in that comprise the following steps：
(1) to PPG and trimethylolpropane reflux dewatering under 130~140 DEG C of high temperature；
(2) less than 80 DEG C are cooled to, it is anti-then to put into dimethylbenzene, methyl diphenylene diisocyanate monomer progress melt polymerization
Should, in 65~80 DEG C of insulations, react 1-3h；
(3) sample, with di-n-butylamine method detection architecture-NCO content, cool after reaching requirement, add butyl acetate, stream
Flat agent and defoamer, filtering and discharging after disperseing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711189238.3A CN107880249A (en) | 2017-11-24 | 2017-11-24 | A kind of polyurethane curing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711189238.3A CN107880249A (en) | 2017-11-24 | 2017-11-24 | A kind of polyurethane curing agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107880249A true CN107880249A (en) | 2018-04-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711189238.3A Pending CN107880249A (en) | 2017-11-24 | 2017-11-24 | A kind of polyurethane curing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107880249A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113234205A (en) * | 2021-06-16 | 2021-08-10 | 北川泰和新材料有限公司 | Polyurethane moisture curing agent high polymer material and production process thereof |
| CN114316175A (en) * | 2021-12-29 | 2022-04-12 | 优麦化学(山东)有限公司 | Solvent-containing isocyanate curing agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618849A (en) * | 2004-01-10 | 2005-05-25 | 广州秀珀化工有限公司 | Low free tolylene diisocynate polyurethane solidifying agent and its preparation method |
| CN102443308A (en) * | 2010-10-15 | 2012-05-09 | 上海维度化工科技有限公司 | Preparation method of epoxy floor paint curing agent |
| CN105153388A (en) * | 2015-09-17 | 2015-12-16 | 广东聚盈化工有限公司 | Single-component low-free TDI humidity polyurethane curing agent and preparation method |
-
2017
- 2017-11-24 CN CN201711189238.3A patent/CN107880249A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618849A (en) * | 2004-01-10 | 2005-05-25 | 广州秀珀化工有限公司 | Low free tolylene diisocynate polyurethane solidifying agent and its preparation method |
| CN102443308A (en) * | 2010-10-15 | 2012-05-09 | 上海维度化工科技有限公司 | Preparation method of epoxy floor paint curing agent |
| CN105153388A (en) * | 2015-09-17 | 2015-12-16 | 广东聚盈化工有限公司 | Single-component low-free TDI humidity polyurethane curing agent and preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113234205A (en) * | 2021-06-16 | 2021-08-10 | 北川泰和新材料有限公司 | Polyurethane moisture curing agent high polymer material and production process thereof |
| CN113234205B (en) * | 2021-06-16 | 2022-07-01 | 北川泰和新材料有限公司 | Polyurethane moisture curing agent high polymer material and production process thereof |
| CN114316175A (en) * | 2021-12-29 | 2022-04-12 | 优麦化学(山东)有限公司 | Solvent-containing isocyanate curing agent and preparation method thereof |
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| PB01 | Publication | ||
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Application publication date: 20180406 |