CN108409940A - A kind of preparation method for the modification MDI being used to prepare high rebound foam - Google Patents
A kind of preparation method for the modification MDI being used to prepare high rebound foam Download PDFInfo
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- CN108409940A CN108409940A CN201810207981.5A CN201810207981A CN108409940A CN 108409940 A CN108409940 A CN 108409940A CN 201810207981 A CN201810207981 A CN 201810207981A CN 108409940 A CN108409940 A CN 108409940A
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- mdi
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- polyether polyol
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
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 present invention relates to a kind of preparation methods for the modification MDI being used to prepare high rebound foam, include the following steps：1) MDI heatings are dissolved, polyether polyol is added dropwise thereto under stirring condition afterwards, the addition of polyether polyol is 15~20wt% of MDI, control system reaction temperature is 60~80 DEG C during dropwise addition, continue constant temperature after being added dropwise to be stirred to react, being considered as reaction when system temperature declines terminates；2) it is added after 2,4'MDI into step 1) system after reaction and carries out physical mixed, 2,4'MDI addition is 30~80wt% of MDI in step 1)；3) be added polymeric MDI into the system after step 2) physical mixed, the content of NCO is 28~31wt% in regulation system, degree of functionality be 2.5~2.8 to get.
Description
Technical field
The present invention relates to the preparation method of modified MDI a kind of more particularly to a kind of modifications being used to prepare high rebound foam
The preparation method of MDI belongs to the production technical field of polyurethane.
Background technology
Existing modified MDI is prolonged to the technology of common MDI -100 and polymeric MDI product currently on the market in the world
It stretches, according to product structure design, the difference of synthesis technology, unique use and processing performance can be provided, to extensive use
In fields such as soft bubble, elastomer, coating, binders.
High rebound foam is mainly used in automotive seat and top-grade furniture, and compared to common soft bubble, high rebound foam has
Higher elasticity, relatively good comfort and performance lasting.High rebound foam currently on the market is using modified MDI and to gather
Ethoxylated polyhydric alcohol, polyester polyol reaction are made after generating polyurethane through foaming, the high elastic modified foam production in south China, East China market
Product using it is commonplace be Huntsman2412,2424,2456 and DOW company NE141, NE135 model modification MDI,
His modification MDI products such as BASF AG 9200, brocade three well CG -63S of lake etc. also have certain application, and the modification of above-mentioned model
Its NCO content of MDI produces the extrudate density of foaming gained after polyurethane usually in 25.5-26.1wt% or so using it
Usually in 45Kg/m3More than, the weight of product unit volume under the density is high, thus production cost and energy consumption are all high.
Invention content
The present invention provides a kind of modification being used to prepare high rebound foam for deficiency existing for existing modified MDI products
The preparation method of MDI.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A kind of preparation method for the modification MDI being used to prepare high rebound foam, includes the following steps：
1) by MDI heating dissolve, after polyether polyol, the addition of polyether polyol is added dropwise thereto under stirring condition
For 15~20wt% of MDI, control system reaction temperature is 60~80 DEG C during dropwise addition, continues constant temperature stirring after being added dropwise
It reacts, being considered as reaction when system temperature declines terminates；
2) it is added after 2,4'-MDI into step 1) system after reaction and carries out physical mixed, 2,4'-MDI addition
Amount is 30~80wt% of MDI in step 1)；
3) be added polymeric MDI into the system after step 2) physical mixed, in regulation system the content of NCO be 28~
31wt%, degree of functionality be 2.5~2.8 to get.
Further, the molal weight of polyether polyol described in step 1) be 3000~5000g/mol, hydroxyl value be 30~
50mgKOH/g。
Further, polyether polyol described in step 1) be PolyTHF ethoxylated polyhydric alcohol, polypropylene oxide ethoxylated polyhydric alcohol,
Any one in polyethylene glycol.
Further, PM400, PM200 of the preferred Wan Hua chemical companies production of the polymeric MDI, the PAPI-27 of DOW Chemical
Any one in product.
The beneficial effects of the invention are as follows：
The use of its NCO content of MDI products that the method for the present invention is modified is 28~31wt%, is sold on the market than existing
The modification MDI products sold improve 3~5 percentage points, thus keep the modification MDI being obtained by the present invention poly- with polyalcohol
It is 30~35kg/m to close the extrudate density through foaming gained after obtaining polyurethane3So that the quality of item of same volume is able to greatly
Amplitude reduction, to achieve the purpose that reduce cost and energy consumption.
Specific implementation mode
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
Embodiment 1：
A kind of preparation method of modified MDI, includes the following steps：
1) by ten thousand China chemistry MDI-100 heating dissolve, after be added dropwise thereto under stirring condition molal weight be 3000
~5000g/mol, the PolyTHF ethoxylated polyhydric alcohol that hydroxyl value is 30~40mgKOH/g, the addition of PolyTHF ethoxylated polyhydric alcohol
Amount is the 15wt% of MDI, and control system reaction temperature is 60~80 DEG C during dropwise addition, and it is anti-to continue constant temperature stirring after being added dropwise
It answers, being considered as reaction when system temperature declines terminates；
2) it is added after 2,4'-MDI into step 1) system after reaction and carries out physical mixed, 2,4'-MDI addition
Amount is the 30wt% of MDI in step 1)；
3) it is added the PM200 of ten thousand magnificent chemical productions into the system after step 2) physical mixed, NCO's contains in regulation system
Amount be 28~31%, degree of functionality be 2.5~2.8 to get.
Embodiment 2：
A kind of preparation method of modified MDI, includes the following steps：
1) by ten thousand China chemistry MDI-100 heating dissolve, after be added dropwise thereto under stirring condition molal weight be 3000
~5000g/mol, the polypropylene oxide ethoxylated polyhydric alcohol that hydroxyl value is 40~50mgKOH/g, the addition of polypropylene oxide ethoxylated polyhydric alcohol
Amount is the 20wt% of MDI, and control system reaction temperature is 60~80 DEG C during dropwise addition, and it is anti-to continue constant temperature stirring after being added dropwise
It answers, being considered as reaction when system temperature declines terminates；
2) it is added after 2,4'-MDI into step 1) system after reaction and carries out physical mixed, 2,4'-MDI addition
Amount is the 50wt% of MDI in step 1)；
3) the PAPI-27 polymeric MDIs of DOW Chemical are added into the system after step 2) physical mixed, in regulation system
The content of NCO be 28~31%, degree of functionality be 2.5~2.8 to get.
Embodiment 3：
A kind of preparation method of modified MDI, includes the following steps：
1) by ten thousand China chemistry MDI-100 heating dissolve, after be added dropwise thereto under stirring condition molal weight be 3000
~5000g/mol, the polyethylene glycol that hydroxyl value is 40~50mgKOH/g, the addition of polyethylene glycol are the 20wt% of MDI, are added dropwise
Control system reaction temperature is 60~80 DEG C in the process, continues constant temperature after being added dropwise and is stirred to react, when system temperature declines
It is considered as reaction to terminate；
2) it is added after 2,4'-MDI into step 1) system after reaction and carries out physical mixed, 2,4'-MDI addition
Amount is the 80wt% of MDI in step 1)；
3) it is added the PM400 of Yantai Wanhua company production into the system after step 2) physical mixed, NCO in regulation system
Content be 28~31wt%, degree of functionality be 2.5~2.8 to get.
1 resulting product of embodiment and the product physical parameter comparison of Huntsman companies in the market are as shown in table 1.
1 embodiment of table, 1 product and the physical parameter of Huntsman2412 products compare
| Appearance | Viscosity (25 DEG C) mPa.s | NCO content | |
| 1 product of embodiment | Brown liquid | 110-150 | 28-30 |
| Huntsman2412 | Brown liquid | 160 | 26.1 |
We are using the modification MDI of 1 gained of embodiment as B component, with component A according to weight ratio (40~45)：100 ratio
Example is added in foaming machine, and material temperature is controlled at 25 DEG C, is injected in mold, is obtained product, the formula of wherein component A is as follows：China
60 parts by weight of three-functionality-degree polyethers 330N of Petrochemical Group Shanghai Gaoqiao petrochemical iy produced；Sinopec Group Shanghai Gaoqiao petrochemical industry
36/2830 parts by weight of three-functionality-degree polyethers of production；0.8 parts by weight of triethanolamine；0.78 parts by weight of catalyst；Mei Side companies
0.3 parts by weight of AK7719 types silicone oil；2.8 parts by weight of water.
We by the product obtained according to the method described above respectively according to GT/T 10808-1989 and GB/T6344-1996 into
Tearing of having gone is tested and stretching experiment, and as a result respectively as shown in table 2 and table 3, while it is 33.7kg/m to measure its density3, falling sphere
Rebound degree is 43%.
The tearing experimental result of 2 product of table
| Testing time | Thickness/mm | Maximum, force/N | Tearing strength/N/cm |
| 1 | 24.4 | 7.25 | 0.29 |
| 2 | 24.5 | 7.49 | 0.3 |
| 3 | 24.8 | 7.33 | 0.29 |
| 4 | 24.2 | 7.6 | 0.3 |
| 5 | 24.9 | 7.71 | 0.31 |
| Standard deviation | 0.37 | 0.01 |
The Tensile Test Results of 3 product of table
Modification MDI it can be seen from above-mentioned experimental results obtained by the method for the present invention is reacted with polyether polyol
Foaming resulting product density is down to 33.7kg/m afterwards3, production cost and energy consumption, and its tear-proof and tensile property can be greatly reduced
Good, falling-rebounding ball rate has fully met the use demand of automotive seat and top-grade furniture up to 43%.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of preparation method for the modification MDI being used to prepare high rebound foam, which is characterized in that include the following steps：
1) by MDI heating dissolve, after polyether polyol is added dropwise thereto under stirring condition, the addition of polyether polyol is
15~20wt% of MDI, control system reaction temperature is 60~80 DEG C during dropwise addition, and it is anti-to continue constant temperature stirring after being added dropwise
It answers, being considered as reaction when system temperature declines terminates；
2) it is added after 2,4'-MDI into step 1) system after reaction and carries out physical mixed, 2,4'-MDI addition is
30~80wt% of MDI in step 1)；
3) it is added polymeric MDI into the system after step 2) physical mixed, the content of NCO is 28~31wt% in regulation system,
Degree of functionality be 2.5~2.8 to get.
2. preparation method according to claim 1, which is characterized in that the molal weight of polyether polyol described in step 1)
For 3000~5000g/mol, hydroxyl value is 30~50mgKOH/g.
3. preparation method according to claim 1, which is characterized in that polyether polyol described in step 1) is poly- tetrahydrochysene furan
Any one muttered in ethoxylated polyhydric alcohol, polypropylene oxide ethoxylated polyhydric alcohol, polyethylene glycol.
4. preparation method according to claim 1, which is characterized in that polymeric MDI described in step 3) is that ten thousand China's chemistry are public
The PM400 or PM200 of production are taken charge of, any one in the PAPI-27 products of Tao Shi DOW Chemicals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810207981.5A CN108409940B (en) | 2018-03-14 | 2018-03-14 | Preparation method of modified MDI (diphenylmethane diisocyanate) for preparing high-resilience foam |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810207981.5A CN108409940B (en) | 2018-03-14 | 2018-03-14 | Preparation method of modified MDI (diphenylmethane diisocyanate) for preparing high-resilience foam |
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| Publication Number | Publication Date |
|---|---|
| CN108409940A true CN108409940A (en) | 2018-08-17 |
| CN108409940B CN108409940B (en) | 2021-04-27 |
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| CN201810207981.5A Active CN108409940B (en) | 2018-03-14 | 2018-03-14 | Preparation method of modified MDI (diphenylmethane diisocyanate) for preparing high-resilience foam |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020260145A1 (en) * | 2019-06-26 | 2020-12-30 | Huntsman International Llc | Process for making a flexible polyurethane foam having a hardness gradient |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020260145A1 (en) * | 2019-06-26 | 2020-12-30 | Huntsman International Llc | Process for making a flexible polyurethane foam having a hardness gradient |
| CN113993925A (en) * | 2019-06-26 | 2022-01-28 | 亨茨曼国际有限公司 | Process for preparing flexible polyurethane foams having a hardness gradient |
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| Publication number | Publication date |
|---|---|
| CN108409940B (en) | 2021-04-27 |
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