CN108794725A - A kind of amino-silane terminated SPU polymer and preparation method thereof - Google Patents
A kind of amino-silane terminated SPU polymer and preparation method thereof Download PDFInfo
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- CN108794725A CN108794725A CN201810329762.4A CN201810329762A CN108794725A CN 108794725 A CN108794725 A CN 108794725A CN 201810329762 A CN201810329762 A CN 201810329762A CN 108794725 A CN108794725 A CN 108794725A
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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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
-
- 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
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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
- C08G18/28—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
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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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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 amino-silane terminated SPU polymer and preparation method thereof, the preparation method of amino-silane terminated SPU polymer of the invention is first to prepare a kind of secondary amino silanes, is then blocked with its opposite end NCO performed polymers.Due to that cannot continue to react again after secondary amino group and NCO group reaction, while the generation of hydrogen bond can be also reduced, therefore the amino-silane terminated SPU polymer compared with low viscosity can finally be prepared.
Description
Technical field
The present invention relates to SPU polymer arts, and in particular to a kind of amino-silane terminated SPU polymer and its preparation side
Method.
Background technology
Silicane-modified polyurethane is also known as SPU polymer, is that one kind being capable of the quick-setting resin of room-temperature moisture.It is to big portion
Divide base material to all have preferable adhesive property, while there is larger elongation at break and lower modulus, is mainly used in and builds
Build sealing and Automatic manual transmission field.
SPU polymer combines the advantage of both silicone adhesive and polyurethane adhesive, while compensating for respective deficiency, very much
Field can substitute the two and use completely, and show more excellent comprehensive performance.The structure of wherein siloxy can
Enough cohesive strengths and adhesive property are provided, while being different from silicone adhesive, the ehter bond in molecular backbone and other poles
Property group can make coating and paint good attachment, have excellent paintability, relative to polyurethane adhesive, SPU polymer
It will not foam in the curing process and toxicity is low.The performance of three is more as shown in table 1 below.
Table 1
| Cementability | Covering with paint property | Operability | Elasticity | Weatherability | The feature of environmental protection | Heat resistance | Storage characteristics | |
| 107 glue | + | -/ | + | + | ++ | ++ | ++ | + |
| Polyurethane adhesive | + | + | - | + | - | - | - | - |
| SPU polymer | ++ | + | + | + | + | ++ | - | ++ |
Wherein：+ indicate；++ it is very good to indicate；Indicate general；/ indicate poor
The preparation method of the amino-silane terminated SPU polymer of tradition is on the basis of preparing end NCO performed polymers, using ammonia
Base silane such as KH550 carries out end capping reaction.Since the reactivity of amino and end NCO performed polymers is high, and react the urea generated
Key, which can continue to react with NCO group under the effect of the catalyst, generates biuret, therefore generally requires control in lower temperature
It is blocked under degree, while strictly to control the charging rate of amino silane, prevented heat release in reaction process from side reaction occurs, hand over
The risk of connection or gel is high, is unfavorable for mass producing.But even if side reaction can be controlled very well, generated after sealing end
Urea bond also easily forms hydrogen bond, causes system viscosity high, generally in 100000mPa.s or more.
Invention content
To solve problems of the prior art, a kind of amino-silane terminated SPU polymer of present invention offer and its system
Preparation Method.The preparation method of the amino-silane terminated SPU polymer of the present invention is first to prepare a kind of secondary amino silanes, then uses it
Opposite end NCO performed polymers are blocked.Due to that cannot continue to react again after secondary amino group and NCO group reaction, while can also reduce
The generation of hydrogen bond, therefore the amino-silane terminated SPU polymer compared with low viscosity can finally be prepared.
Specifically, the preparation method of the amino-silane terminated SPU polymer of the present invention, is blocked with secondary amino silanes.
The preparation method of the amino-silane terminated SPU polymer of the present invention, includes the following steps：
1000 parts by weight macromolecule polyethers, 27.9~35.7 parts by weight of toluene diisocyanate are added into reaction kettle
(TDI) or 35.6~45.6 parts by weight isoflurane chalcone diisocyanates (IPDI), 0.07~0.12 parts by weight tin dilaurate, two fourth
Ji Xi (DBTDL) stirs and is warming up to 38~65 DEG C of 4~6h of reaction, secondary amino silanes stirring is then added into reaction kettle, instead
Should up to using standard acetone di-n-butylamine titration there is no NCO group in the presence of, that is, obtain described amino-silane terminated
SPU polymer.
Wherein, the purpose that secondary amino silanes are added is for blocking, and addition is not particularly limited, preferably 43-97 weight
Part.
Wherein, the secondary amino silanes are prepared by following methods：
Using KH550 and acrylic ester compound as raw material, 3~7h is stirred to react at 10~60 DEG C, vacuum distillation removes
Excess reactant obtains clear viscous shape liquid.
In addition, the molar ratio of the KH550 and acrylic ester compound is 1：0.9~1.2.
Wherein, KH550 can also use union carbide corporation of U.S. A -1100, Japan SHIN-ETSU HANTOTAI KBM-903 to replace, the change of KH550
Scientific name is known as γ-aminopropyl triethoxysilane, 3- aminopropyl triethoxysilanes or 3-APTS.
In addition, the acrylic ester compound is methyl acrylate, butyl acrylate, isobornyl acrylate, propylene
Any one in the different monooctyl ester of acid, 3- trimethoxy silane propyl acrylates.
In addition, KH550 and acrylic ester compound are added in reaction kettle simultaneously or incited somebody to action by bottom material of one of which
Another kind is added drop-wise in reaction kettle.
In addition, the macromolecule polyethers hydroxyl value is 10mg KOH/g.
Further, the macromolecule polyethers is PPG12000.
The present invention also provides amino-silane terminated SPU polymer made from a kind of preparation method as described above.
Relative to the preparation method of the amino-silane terminated SPU of tradition, synthetic method provided by the present invention has following excellent
Point：(1) structure that will not form biuret can effectively reduce the hydrogen bond in system, and the viscosity of product is low, 20000~
35000mPa.s.(2) do not have to worry gel problem in capping process；(3) closed-end efficiency is high, and 1h or so can complete to block；(4) divide
Son amount distribution is uniform.
Description of the drawings
Fig. 1 is the infrared spectrogram of SPU polymer prepared by Examples 1 to 4.
Fig. 2 is the rheogram of SPU polymer prepared by embodiment 3.
Specific implementation mode
Technical solution of the present invention is discussed in detail with reference to the accompanying drawings and embodiments, but the present invention is not limited to these implementations
Example.
Embodiment 1
It takes 221g (1mol) KH550 and 77.5g (0.9mol) methyl acrylate while being added in reaction kettle, after charging
It is kept for 10 DEG C and is stirred to react 3h, then vacuum distillation removes excess reactant, obtains clear viscous shape liquid.
Be added into reaction kettle 1000g macromolecules polyethers (PPG12000, hydroxyl value are 10mg KOH/g), 27.9g TDI,
0.07g DBTDL stir and are warming up to 38 DEG C of reaction 4h, are then added into reaction kettle prepared secondary in 43.7g step 1
Amino silane be stirred to react until using standard acetone di-n-butylamine titration there is no NCO group in the presence of, you can discharging
The amino-silane terminated SPU polymer of the present invention is obtained, infrared spectrogram is as shown in Figure 1.
Embodiment 2
It takes 221g (1mol) KH550 and 77.5g (0.9mol) methyl acrylate while being added in reaction kettle, after charging
It is kept for 10 DEG C and is stirred to react 3h, then vacuum distillation removes excess reactant, obtains clear viscous shape liquid.
Be added into reaction kettle 1000g macromolecules polyethers (PPG12000, hydroxyl value are 10mg KOH/g), 35.7g TDI,
0.07g DBTDL stir and are warming up to 38 DEG C of reaction 4h, are then added into reaction kettle prepared secondary in 43.7g step 1
Amino silane be stirred to react until using standard acetone di-n-butylamine titration there is no NCO group in the presence of, you can discharging
The amino-silane terminated SPU polymer of the present invention is obtained, infrared spectrogram is as shown in Figure 1.
Embodiment 3
221g (1mol) KH550 and 250g (1.2mol) isobornyl acrylate is taken, acrylic acid is added dropwise by bottom material of KH550
Isobornyl thiocyanoacetate is kept for 60 DEG C after charging and is stirred to react 7h, and then vacuum distillation removes excess reactant, obtains clear viscous
Shape liquid.
1000g macromolecules polyethers (PPG12000, hydroxyl value are 10mg KOH/g), 45.6g are added into reaction kettle
IPDI, 0.12g DBTDL stir and are warming up to 65 DEG C of reaction 6h, be then added into reaction kettle prepared in 97.5g step 1
Secondary amino silanes be stirred to react until using standard acetone di-n-butylamine titration there is no NCO group in the presence of, you can
Discharging obtains the amino-silane terminated SPU polymer of the present invention, and infrared spectrogram is as shown in Figure 1.
Embodiment 4
221g (1mol) KH550 and 1.0mol Isooctyl acrylate monomers are taken, using Isooctyl acrylate monomer as bottom material, KH550 is added dropwise,
It is kept for 30 DEG C after charging and is stirred to react 5h, then vacuum distillation removes excess reactant, obtains clear viscous shape liquid.
1000g macromolecules polyethers (PPG12000, hydroxyl value are 10mg KOH/g), 35.6g are added into reaction kettle
IPDI, 0.09g DBTDL stir and are warming up to 45 DEG C of reaction 5h, are then added into reaction kettle prepared in 86g step 1
Secondary amino silanes be stirred to react until using standard acetone di-n-butylamine titration there is no NCO group in the presence of, you can go out
Material obtains the amino-silane terminated SPU polymer of the present invention, and infrared spectrogram is as shown in Figure 1.
The performance parameter of SPU polymer prepared by the present invention is as described in Table 1.
Table 1
Application examples 1：
Using SPU polymer prepared in embodiment 3, carried out according to formula as shown in table 2 below using planetary mixer
It is uniformly mixed and deaeration, rheogram is as shown in Figure 2.
Table 2
According to iso standard (ISO37 after curing 7 days:2011/ISO868:2003/ASTM D2377:2014) to its performance
It is tested, as a result as shown in table 3 below.
Table 3
| Performance | Test result |
| Surface drying time (min) | 200 |
| Tensile strength (MPa) | 2.8 |
| Elongation at break (%) | 270 |
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's
Within protection domain.
Claims (9)
1. a kind of preparation method of amino-silane terminated SPU polymer, which is characterized in that blocked with secondary amino silanes.
2. preparation method according to claim 1, which is characterized in that include the following steps：
1000 parts by weight macromolecule polyethers, 27.9~35.7 parts by weight of toluene diisocyanate (TDI) are added into reaction kettle
Or 35.6~45.6 parts by weight isoflurane chalcone diisocyanates (IPDI), 0.07~0.12 parts by weight dibutyl tin laurate
(DBTDL), 38~65 DEG C of 4~6h of reaction are stirred and be warming up to, secondary amino silanes stirring are then added into reaction kettle, reaction is straight
To the acetone di-n-butylamine titration using standard there is no NCO group in the presence of, that is, it is poly- to obtain the amino-silane terminated SPU
Close object.
3. preparation method according to claim 2, which is characterized in that the secondary amino silanes are prepared by following methods：
Using KH550 and acrylic ester compound as raw material, 3~7h is stirred to react at 10~60 DEG C, it is extra that vacuum distillation removes
Reactant obtains clear viscous shape liquid.
4. preparation method according to claim 3, which is characterized in that the KH550 and acrylic ester compound rub
You are than being 1：0.9~1.2.
5. preparation method according to claim 3, which is characterized in that the acrylic ester compound is acrylic acid first
It is any one in ester, butyl acrylate, isobornyl acrylate, Isooctyl acrylate monomer, 3- trimethoxy silane propyl acrylates
Kind.
6. preparation method according to claim 3, which is characterized in that add KH550 and acrylic ester compound simultaneously
Enter in reaction kettle or another kind is added drop-wise in reaction kettle using one of which as bottom material.
7. preparation method according to claim 3, which is characterized in that the macromolecule polyethers hydroxyl value is 10mg KOH/
g。
8. preparation method according to claim 7, which is characterized in that the macromolecule polyethers is PPG12000.
9. amino-silane terminated SPU polymer made from a kind of preparation method as described in any one of claim 1-8.
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| CN201810329762.4A CN108794725A (en) | 2018-04-13 | 2018-04-13 | A kind of amino-silane terminated SPU polymer and preparation method thereof |
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| CN201810329762.4A CN108794725A (en) | 2018-04-13 | 2018-04-13 | A kind of amino-silane terminated SPU polymer and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4067844A (en) * | 1976-12-22 | 1978-01-10 | Tremco Incorporated | Urethane polymers and sealant compositions containing the same |
| CN1974580A (en) * | 2006-12-06 | 2007-06-06 | 华南理工大学 | Prepn process of acrylate modified gamma-aminopropyl triethoxysilane |
| CN103694946A (en) * | 2013-12-20 | 2014-04-02 | 湖北新蓝天新材料股份有限公司 | Method for producing silane modified polyurethane sealant by using secondary amino alpha-silane |
| CN103910847A (en) * | 2014-03-19 | 2014-07-09 | 华南理工大学 | Silane terminated polyurethane oligomer and its preparation method |
-
2018
- 2018-04-13 CN CN201810329762.4A patent/CN108794725A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4067844A (en) * | 1976-12-22 | 1978-01-10 | Tremco Incorporated | Urethane polymers and sealant compositions containing the same |
| CN1974580A (en) * | 2006-12-06 | 2007-06-06 | 华南理工大学 | Prepn process of acrylate modified gamma-aminopropyl triethoxysilane |
| CN103694946A (en) * | 2013-12-20 | 2014-04-02 | 湖北新蓝天新材料股份有限公司 | Method for producing silane modified polyurethane sealant by using secondary amino alpha-silane |
| CN103910847A (en) * | 2014-03-19 | 2014-07-09 | 华南理工大学 | Silane terminated polyurethane oligomer and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 姚晓宁: "SPU密封胶的制备及结构与力学性能关系的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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Effective date of registration: 20190617 Address after: 332000 Yang Jia Ling, Yongxiu County, Jiujiang, Jiangxi Applicant after: JIANGXI BLUESTAR XINGHUO ORGANIC SILICONE CO., LTD. Address before: 214000 Jiangsu Wuxi Huishan industrial transformation cluster area north Hui Road Applicant before: Wuxi Long Chi fluorosilicone New Material Co., Ltd. |
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Application publication date: 20181113 |