CN105018015B - Method for preparing polyurethane-modified organosilicon double-component room-curing elastomer adhesive - Google Patents
Method for preparing polyurethane-modified organosilicon double-component room-curing elastomer adhesive Download PDFInfo
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- CN105018015B CN105018015B CN201510470146.7A CN201510470146A CN105018015B CN 105018015 B CN105018015 B CN 105018015B CN 201510470146 A CN201510470146 A CN 201510470146A CN 105018015 B CN105018015 B CN 105018015B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000806 elastomer Substances 0.000 title claims abstract description 24
- 239000000853 adhesive Substances 0.000 title claims abstract description 23
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- -1 polysiloxane Polymers 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 229920002545 silicone oil Polymers 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 8
- 239000013530 defoamer Substances 0.000 claims description 7
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 230000011218 segmentation Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 7
- 229920001296 polysiloxane Polymers 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 abstract 1
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- 239000012975 dibutyltin dilaurate Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229920001228 polyisocyanate Polymers 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 description 13
- 229920002635 polyurethane Polymers 0.000 description 12
- 238000001723 curing Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910018557 Si O Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000004017 vitrification Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 244000144992 flock Species 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000005284 basis set Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WOZUGDXHVLSOHV-UHFFFAOYSA-L dodecanoate tin(4+) Chemical compound [Sn+4].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].[Sn+4] WOZUGDXHVLSOHV-UHFFFAOYSA-L 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 238000006897 homolysis reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920000260 silastic Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a method for preparing a polyurethane-modified organosilicon double-component room-curing elastomer adhesive, which comprises the following steps: (1) uniformly mixing hydroxypropyl-terminated silicone oil and glycerol, and dehydrating to obtain a hydroxyl-terminated (-OH) component; (2) reacting aromatic polyisocyanate, the hydroxyl-terminated (-OH) component and dibutyltin dilaurate to obtain a component A; (3) adding vapor-phase silica white, carbon black and talcum powder into the container filled with hydroxy silicone oil and dihydroxy polysiloxane, adding a catalyst, adding 3-aminopropyl triethoxy silane, finally adding a defoaming agent, uniformly mixing, and drying to obtain a component B; and (4) uniformly mixing the component A and component B in a mass ratio of 12:(23.5-24), and curing at room temperature for 4-5 hours. The elastomer adhesive prepared by the method has the advantages of favorable tear resistance, excellent high/low temperature resistance and excellent binding property. The preparation method is easy to operate and accessible in raw materials, and lowers the preparation cost.
Description
Technical field
The present invention relates to one kind prepare polyurethane-modified organosilicon double-component cold curing high temperature resistant, it is low temperature resistant, elasticity it is good
The method of the elastomer adhesive of excellent performance, belongs to new chemical materialses technical field.
Background technology
Polyurethane（PU）It is polyurethanes（polyurethane）Abbreviation.It is every to contain perhaps on high polymer main chain
The carbamates (- NH-COO-) for repeating or urea groups more（-NH-CO-NH）The compound of group is referred to as polyurethane.
Polyurethane is by the alternate block polymer of soft section and hard section.The soft section of polyurethane macromolecular is typically by long-chain polyether
Or the soft segment such as polyethers is constituted, in random coil shape.And segmented polyurethane（Rigid chain segment）Then by diisocyanate and two
The chain extenders such as first alcohol, diamine（Or cross-linking agent）Obtain containing aryl, carbamate groups, substituted urea it is basis set into rigid chain
Section, its conformation not malleable, is extended into bar-shaped under room temperature.From from micro-phase action, the rigid chain segment in molecule, due to interior
The reason for cumulative and intermolecular hydrogen bonding, flock together each other, form many hard segment domains junior units, the glass of these junior units
It is higher than room temperature to change temperature, at room temperature in glassy state, para-crystal or crystallite, frequently referred to plastics phase.And the soft segment in strand
Also flock together, because vitrification point is less than room temperature, referred to as rubber phase.Why polyurethane is with microphase-separated knot
Structure, precisely due to the incompatible of the rubber phase of the plastics phase of hard segment structure and soft section is caused, also just because of microphase-separated
Presence just makes polyurethane have excellent performance.In general, the content of rigid chain segment is bigger in polyurethane, soft segment is more soft
It is lower along the vitrification point of soft segment in other words, more it is susceptible to microphase-separated.The performance of polyurethane, generally speaking still
Affected by the morphosiss of macromolecular chain.Unique pliability of polyurethane and the physical property of wide scope can be with biphase
Form carrys out reasonable dismissal.Just because of the microphase-separated of appropriateness, just cause polyurethane elastomer that there is excellent combination property.Example
Such as：Excellent wearability, its wearability is 2～10 times of natural rubber；Higher intensity and elasticity, can be in wider hardness
In the range of keep higher elasticity, and under same rigidity, grease resistance higher than the bearing capacity of other elastomers and chemicals-resistant
Function admirable, oxygen resistence and ozone resistance are excellent, fatigue durability and freedom from vibration are good.
Organosilicon is referred in molecular structure main chain and contains elemental silicon（Si）, and connect the polymer of organic group on Si.Generally
Refer to polysiloxane (abbreviation polysiloxanes silicones), it is to connect based on Si-O keys to repeat alternately constitute stable bone
The polymer of frame.They have half inorganic, half organic structure macromolecular compound, have organic polymer and inorganic polymer concurrently
Characteristic.Therefore organosilicon material has diversification performance, and the group of connection is different, and it is substantially poor also to have in its performance
It is different, so it is generally acknowledged that it has organic and inorganic material two-fold advantage concurrently.This is also why organosilicon has perhaps in performance
Where many uniquenesses.
The main determining factor of the thermostability of organosilicon is determined by the size of interatomic covalent bond, so polysiloxanes note
Surely there is good heat stability.This is because the bond energy of covalent bond Si-O is higher by 115KJ/ than the bond energy 347KJ/mol of C-C key
Mol, and the bond energy of Si-C keys is also very high, and simple warm-up movement is difficult to make Si-O keys and Si-C keys that homolysis to occur.Again due to silicon
With the difference in oxygen electronegativity, shielding action can be played to connected alkyl, even more improve its oxidation stability.
It is long that there is organosilicon excellent low-temperature flexibility to be primarily due to Si-O bond lengths, and bond angle is big, flexible, glutinous stream activation
What can be low the reason for, caused.Such as：PolydimethylsiloxaneChain Chain section is quite submissive, when temperature is at -136 DEG C, however it remains segment
Motion.Silastic copolymer containing phenyl can significantly reduce vitrification point, and the resistance to low temperature of silicone rubber navigates in aviation
It application fully develops talents.
The content of the invention
For polyurethane high temperature resistant poor performance, and organosilicon material bonds bad shortcoming, it is an object of the invention to provide
A kind of method for preparing polyurethane-modified organosilicon double-component cold curing elastomer adhesive.Elastomer precursor gum prepared by this method
Stick has a good tear resistance, excellent high and low temperature resistance and caking property, and preparation method is easily operated, former material used
Material is easy to get, and reduces preparation cost.
The technical scheme is that what is be achieved in that：
The method for preparing polyurethane-modified organosilicon double-component cold curing elastomer adhesive, step is as follows,
（1）Raw material prepares：By the end hydroxypropyl silicone oil of relative average molecular mass Mw=1000 and glycerol according to mass ratio
20~22:1 than row mix homogeneously, mixture under the conditions of 100 DEG C ~ 110 DEG C through vacuum dehydration process 3 ~ 4h, obtain aqueous
Terminal hydroxy group of the amount below 0.05%（-OH）Component；
（2）It is prepared by component A：By aromatic poly-isocyanate, step（1）The terminal hydroxy group for obtaining（-OH）Component presses functional group n
（NCO/OH）=1.8 ~ 1.82, catalyst dibutyltin dilaurylate addition be the component A gross mass for finally obtaining 0.05% ~
0.06% dispensing, reacts after 4 ~ 4.5h at 58 ~ 62 DEG C of reaction temperature and discharges, obtain-NCO content is that 4.8 ~ 5.0%, viscosity is
The component A of 8000 ~ 8200mPa.s；
（3）It is prepared by B component：By the gas-phase silica processed through silazane, thin white carbon black and cunning are fully ground in advance
Stone powder is added in the container equipped with hydroxy silicon oil and polysiloxanediol, is added by dibutyl tin laurate and three second
The mixed catalyst that amine is constituted, stirring 1h makes its mix homogeneously；3- aminopropyl triethoxysilanes stirring 1h is subsequently adding, finally
After adding defoamer stirring 2h mix homogeneously, it is put in vacuum drying oven 90 DEG C and is dried 3h ~ 3.5 h and obtain final product B component；
Wherein gas-phase silica, white carbon black, Pulvis Talci, hydroxy silicon oil, polysiloxanediol, mixed catalyst, 3- ammonia third
Ethyl triethoxy silicane alkane and defoamer are respectively（3）5% ~ 6%, 7% ~ 8%, the 2% of the B component gross mass that step is prepared ~
2.5%、9%~9.5%、70%~74%、0.05~0.06%、2%~2.2%、4.3%~4.5%；
（4）It is prepared by elastomer adhesive：By step（2）（3）Obtained component A and B component in mass ratio 12:23.5~24
4 ~ 5h of cold curing obtains final product final elastomer adhesive after mix homogeneously.
Preferably, reacted using nitrogen protection when preparing component A, before reaction starts, be passed through dry nitrogen by container
Air exclude clean, be passed through nitrogen until reaction terminates stopping.
Preferably, step（2）When preparing component A, terminal hydroxy group（-OH）Component is added using segmentation Deca mode；First paragraph
Add terminal hydroxy group（-OH）The 1/3 ~ 1/2 of amounts of components, rate of addition control in 20 drops/min, after being added dropwise to complete reaction 8 ~
10min；Second segment adds terminal hydroxy group（-OH）The 1/3 of amounts of components, rate of addition 15 drips/min, and 10min is reacted after being added dropwise to complete
Left and right；The 3rd section of remaining terminal hydroxy group of Deca（-OH）Component, rate of addition is controlled in 20 drops/min, until completion of dropping；Charging
After the completion of react again after 4h ~ 4.5h discharge；Reaction temperature is controlled at 58 ~ 62 DEG C in charging and course of reaction.
Step（1）In glycerol can use equal material amount trimethylolpropane replace.
Step（1）In end hydroxypropyl silicone oil can use equal material amount relative average molecular mass Mw=600 poly- second
Glycol is replacing.
The（1）The described glycerol of step is the material of trifunctional.
Compared to existing technology, the present invention has the advantages that：
1）The present invention prepares double-component cold curing elastomer adhesive, and the method is easy to operate in building-up process, production
Cycle is short, product has good tear resistance and high and low temperature resistance, it is easy to carry, cold curing, easy construction.
2）Using the method for previously prepared end-NCO performed polymers to reduce aromatic poly-isocyanate in high NCO content, from
And its toxicity is reduced, and after the more excellent process conditions of control ratio, the product of high conversion can be obtained, whole process is easily operated
And solvent-free addition.
3）Using triethylamine and dibutyl tin laurate as catalyst, although the single fourth of organic tin tin dilaurate two
Base tin catalyst is higher with the catalytic reaction activity of OH groups to NCO group than tertiary amines Triethylamine catalyst, but both add jointly
Entering the catalyst effect more double than single any one will be good, and triethylamine price is relatively cheap, reduces material
Cost.
4）There are fume colloidal silica and precipitated silica active filler may be selected in the preparation of B component, Linesless charcoal black track producing particle
The stronger absorption base rubber in surface strand, the usual white carbon particle surface first line of a couplet is connected to several strands, forms chain
Between physical crosslinking, and the Linesless charcoal black track producing particle of binding molecule chain can also play a part of uniformly distributed.Experiment finds, in gas
In the selection of phase white carbon and precipitated silica, gas-phase silica is more excellent.This is because gas-phase silica purity is high, specific surface
Product is big, and particle diameter is little, good to the reinforcing effect of organosilicon.And precipitated silica is then conversely, and easily produce foaming during molding
The shortcomings of phenomenon, hot-air cure difficulty.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment.
The present invention prepares the method for double-component cold curing method elastomer adhesive and comprises the following steps：
（1）Raw material prepares：By end hydroxypropyl silicone oil（Relative average molecular mass Mw=1000）Exist with the mixture of glycerol
Reaction processes 3 ~ 4h under the conditions of 100 DEG C ~ 110 DEG C through vacuum dehydration in advance before starting, and obtains water content below 0.05%
Terminal hydroxy group（-OH）Component.Both mixing quality ratios are 20 ~ 22:1.
（2）It is prepared by component A：By aromatic poly-isocyanate, terminal hydroxy group（-OH）Component（End hydroxypropyl silicone oil and glycerol）
By functional group n（NCO/OH）=1.8 ~ 1.82, catalyst dibutyltin dilaurylate addition for component A gross mass 0.05% ~
0.06% dispensing, reacts after the h of 4h ~ 4.5 at 58 DEG C ~ 62 DEG C of reaction temperature and discharges, obtain-NCO content is 4.8 ~ 5.0%, viscosity
For the component A of 8000 ~ 8200mPa.s；
（3）It is prepared by B component：Account for B component total amount 5% ~ 6% through silazane（Hexamethyldisiloxane）The gas for processing
Phase white carbon, the white carbon black that thin 7% ~ 8% is fully ground in advance and 2% ~ 2.5% Pulvis Talci are added to equipped with 9% ~ 9.5% hydroxyl silicon
Oil（The actual trade mark is 203）Polysiloxanediol with 72% ~ 74%（107 glue）In container, 0.05 ~ 0.06% is eventually adding
The mixed catalyst being made up of dibutyl tin laurate and triethylamine, dibutyl tin laurate and triethylamine mass ratio are 2：
1 high-speed stirred 1h makes its mixing substantially uniformity.Add 2% ~ 2.2% 3- aminopropyl triethoxysilanes（Silane coupler
KH-550）High-speed stirred 1h, is eventually adding 4.3% ~ 4.5% defoamer high-speed stirred 2h, is put in vacuum drying oven 90 DEG C and does
Dry 3h ~ 3.5 h obtains final product B component.
（4）It is prepared by elastomer adhesive：Will be above-mentioned（2）（3）Obtained adhesive AB components in mass ratio 12:23.5~24
4 ~ 5h of cold curing is obtained elastomer after mix homogeneously.
Wherein：The（1）During the raw material of step prepares, the water content of polyols blend must be below 0.05%, because there is water
Its meeting of words generates CO with the NCO functional group reactionses in raw material2Gas, so as to cause the consumption of main material, so that after having influence on
The mechanical property of facestock material.The（1）Step raw material prepares to compare a condition of optimization：It is de- through vacuum under the conditions of 110 DEG C
Water process 3h, water is not easy removing completely or dewatering time is long when temperature is too low.
Step（1）In glycerol can use equal material amount trimethylolpropane（TMP）Replace；Same step（1）
In end hydroxypropyl silicone oil can be replaced with the Polyethylene Glycol of the relative average molecular mass Mw=600 of the amount of equal material.
The（2）Step component A synthesis ratio compared with optimization a condition be：Aromatic poly-isocyanate, end hydroxypropyl silicone oil
Functional group n is pressed with glycerol（NCO/OH）=1.8, more preferably mass ratio is three's ratio：Aromatic poly-isocyanate：End hydroxypropyl
Base silicone oil：Glycerol=50:63.5:2.9.Catalyst dibutyltin dilaurylate addition is the 0.05% of component A gross mass, instead
Answer temperature 60 C and response time 4h, higher temperature that the molecular weight of product can be made to sharply increase and reach or close gel
Point, when temperature is too low-NCO group reaction is incomplete and the response time is long.During base polyurethane prepolymer for use as component A is obtained under the conditions of this
It is 8040mPa.s that NCO residual volumes are 4.86%, viscosity.
The（2）The described glycerol of step is the material of trifunctional, and the presence of polyfunctional group material can generate the knot of build
Structure, crosslink density also can be greatly increased, and this influences whether the hardness and intensity of material；Can be with the polyhydroxy silicon of the amount of equal material
Oil and trimethylolpropane replace.
The（2）The synthesis of step component A, in order to preferably react, can be carried out using segmentation Deca.Using segmentation dropping end hydroxyl
The mixture of propyl group silicone oil and glycerol prepares component A.First paragraph adds the 1/3 ~ 1/2 of amount of mixture, rate of addition control
In 20 drops/min, 8 ~ 10min is reacted after being added dropwise to complete；Second segment continuously adds the 1/3 of amount of mixture, and rate of addition 15 drips/
Min, reacts 10min or so after being added dropwise to complete；3rd section of Deca remaining mixture, rate of addition is controlled in 20 drops/min, until
Completion of dropping.React after the completion of charging after the h of 4h ~ 4.5 and discharge.Reaction temperature is controlled 58 ~ 62 in charging and course of reaction
℃。
Reacted using nitrogen protection when preparing component A, before reaction starts, be passed through dry nitrogen and arrange the air in container
Except clean, until reaction terminates to stop being passed through nitrogen again.
Above-mentioned（3）A quality proportioning of optimization is compared in the preparation of step B component：107 glue：Hydroxy silicon oil 203：February
Dilaurylate：Triethylamine：White carbon black：Pulvis Talci：Defoamer：Gas-phase silica：KH-550=155.4：20：0.1：0.05：
15：5：10：12.6：4.42.Its technical process is：It is fully ground the gas-phase silica processed through silazane and in advance
Thin white carbon black, Pulvis Talci is added to according to the above ratio in the kneader equipped with the glue of a certain amount of hydroxy silicon oil 203 and 107, then is added
Enter catalyst dibutyltin dilaurylate and triethylamine, then vacuum kneading 1h so as to after mixing substantially uniformity, add silane
Coupling agent KH-550 mediates again 1h, is eventually adding defoamer, after mediating 2h, is put in vacuum drying oven 90 DEG C and is dried after 3h and take
Go out, obtain final product B component.
The（3）Step organosilicon B component is processed by the way of stirring, roll-in grinding distribution, reaches sufficiently mixing,
To eliminate very big filler particles.
Above-mentioned（4）A quality proportioning of optimization is compared in the preparation of step adhesive：AB components in mass ratio 12:23.5
Preferably, excessive component A has that unnecessary-NCO is remaining to cold curing 4h, it can and air in reaction of moisture generation CO2Gas
Body, so as to cause material in may have bubble to produce.
The（4）Step is liquid due to component A, and B component is solid paste thing, so B component can take extruding, injection pressure or
The mode that person directly routinely takes out is taken out and is used.
The elastomer adhesive for preparing according to the method described above is good to glassy bond, and elongation at break is more than 400%, fracture
Intensity is more than 3MPa；Heat stability is good, can life-time service at 150 DEG C.
The above embodiment of the present invention is only example to illustrate the invention, and is not the enforcement to the present invention
The restriction of mode.For those of ordinary skill in the field, on the basis of the above description other can also be made not
With the change and variation of form, the change of the length, width and height equivalence of such as sample can be made according to individual demand and change.Here cannot
All of embodiment is exhaustive.It is every to belong to obvious change or the change that technical scheme is amplified out
The dynamic row still in protection scope of the present invention.
Claims (6)
1. the method for preparing polyurethane-modified organosilicon double-component cold curing elastomer adhesive, it is characterised in that：Step is such as
Under,
（1）Raw material prepares：By the end hydroxypropyl silicone oil of relative average molecular mass Mw=1000 and glycerol according to mass ratio 20 ~
22:1 mix homogeneously, mixture processes 3 ~ 4h under the conditions of 100 DEG C ~ 110 DEG C through vacuum dehydration, obtains water content 0.05%
Following terminal hydroxy group（-OH）Component；
（2）It is prepared by component A：By aromatic poly-isocyanate, step（1）The terminal hydroxy group for obtaining（-OH）Component presses functional group n
（NCO/OH）=1.8 ~ 1.82, catalyst dibutyltin dilaurylate addition be the component A gross mass for finally obtaining 0.05% ~
0.06% dispensing, reacts after 4 ~ 4.5h at 58 ~ 62 DEG C of reaction temperature and discharges, obtain-NCO content is that 4.8 ~ 5.0%, viscosity is
The component A of 8000 ~ 8200mPa.s；
（3）It is prepared by B component：By the gas-phase silica processed through silazane, thin white carbon black and Pulvis Talci is fully ground in advance
In being added to the container equipped with hydroxy silicon oil and polysiloxanediol, add by dibutyl tin laurate and triethylamine structure
Into mixed catalyst, stirring 1h make its mix homogeneously；3- aminopropyl triethoxysilanes stirring 1h is subsequently adding, is eventually adding
After defoamer stirring 2h mix homogeneously, it is put in vacuum drying oven 90 DEG C and is dried 3h ~ 3.5 h and obtain final product B component；
Wherein gas-phase silica, white carbon black, Pulvis Talci, hydroxy silicon oil, polysiloxanediol, mixed catalyst, 3- aminopropyls three
Ethoxysilane and defoamer are respectively（3）5% ~ 6%, 7% ~ 8%, 2% ~ 2.5%, the 9% of the B component gross mass that step is prepared ~
9.5%、70%~74%、0.05~0.06%、2%~2.2%、4.3%~4.5%；Each component sum is 100%；
（4）It is prepared by elastomer adhesive：By step（2）（3）Obtained component A and B component in mass ratio 12:23.5 ~ 24 mixing
4 ~ 5h of cold curing obtains final product final elastomer adhesive after uniform.
2. the side for preparing polyurethane-modified organosilicon double-component cold curing elastomer adhesive according to claim 1
Method, it is characterised in that：Reacted using nitrogen protection when preparing component A, before reaction starts, be passed through dry nitrogen by container
Air is excluded totally, and until reaction terminates stopping nitrogen being passed through.
3. the side for preparing polyurethane-modified organosilicon double-component cold curing elastomer adhesive according to claim 1
Method, it is characterised in that：Step（2）When preparing component A, terminal hydroxy group（-OH）Component is added using segmentation Deca mode；First paragraph adds
Enter terminal hydroxy group（-OH）The 1/3 ~ 1/2 of amounts of components, rate of addition is controlled in 20 drops/min, and 8 ~ 10min is reacted after being added dropwise to complete；
Second segment adds terminal hydroxy group（-OH）The 1/3 of amounts of components, rate of addition 15 drips/min, and 10min or so is reacted after being added dropwise to complete；
The 3rd section of remaining terminal hydroxy group of Deca（-OH）Component, rate of addition is controlled in 20 drops/min, until completion of dropping；Charging is completed
React again afterwards and discharged after 4h ~ 4.5h；Reaction temperature is controlled at 58 ~ 62 DEG C in charging and course of reaction.
4. the side for preparing polyurethane-modified organosilicon double-component cold curing elastomer adhesive according to claim 1
Method, it is characterised in that：Step（1）In glycerol replaced with the trimethylolpropane of the amount of equal material.
5. the side for preparing polyurethane-modified organosilicon double-component cold curing elastomer adhesive according to claim 1
Method, it is characterised in that：Step（1）In end hydroxypropyl silicone oil with the relative average molecular mass Mw=600's of the amount of equal material
Polyethylene Glycol is replacing.
6. the side for preparing polyurethane-modified organosilicon double-component cold curing elastomer adhesive according to claim 1
Method, it is characterised in that：The（1）The described glycerol of step is the material of trifunctional.
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| CN106753173B (en) * | 2016-12-15 | 2020-05-01 | 佛山市顺德区国精合成材料有限公司 | Preparation method of modified water-based polyurethane pressure-sensitive adhesive |
| CN106939152B (en) * | 2017-04-20 | 2020-07-31 | 成都龙之泉科技股份有限公司 | Preparation method of flame-retardant temperature-resistant corrosion-resistant adhesive |
| CN109369883A (en) * | 2018-09-01 | 2019-02-22 | 哈尔滨工程大学 | A kind of preparation method of organic silicon modified polyurethane adhesive |
| CN114517015A (en) * | 2020-11-20 | 2022-05-20 | 洛阳尖端技术研究院 | Wave-absorbing composition, wave-absorbing material and preparation method thereof |
| CN114874556B (en) * | 2022-04-15 | 2023-08-25 | 无锡裕德电缆科技有限公司 | Flame-retardant ethylene propylene diene monomer rubber sleeve for cable and preparation method thereof |
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| US5482988A (en) * | 1994-01-14 | 1996-01-09 | Dow Corning Corporation | Hot-melt silicone pressure sensitive adhesive with siloxylated polyether waxes as additives |
| CN1597824A (en) * | 2004-08-23 | 2005-03-23 | 浙江大学 | Sealing glue of polyurethane modified organic silicon with good surface coating and preparation process thereof |
| CN102417595A (en) * | 2011-11-20 | 2012-04-18 | 浙江精业生化有限公司 | Preparation method of novel polyurethane-modified organic silica gel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5482988A (en) * | 1994-01-14 | 1996-01-09 | Dow Corning Corporation | Hot-melt silicone pressure sensitive adhesive with siloxylated polyether waxes as additives |
| CN1597824A (en) * | 2004-08-23 | 2005-03-23 | 浙江大学 | Sealing glue of polyurethane modified organic silicon with good surface coating and preparation process thereof |
| CN102417595A (en) * | 2011-11-20 | 2012-04-18 | 浙江精业生化有限公司 | Preparation method of novel polyurethane-modified organic silica gel |
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