CN104817702A - Spherical dendritic organic silicon macromolecule, preparation method thereof and application - Google Patents
Spherical dendritic organic silicon macromolecule, preparation method thereof and application Download PDFInfo
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Abstract
The invention belongs to the field of chemical synthesis, and particularly relates to a spherical dendritic organic silicon macromolecule, a preparation method thereof and an application. The structural formula of the spherical dendritic organic silicon macromolecule is indicated in a formula I. The spherical dendritic organic silicon macromolecule is synthesized by a two-step circulation method, and then the synthesized spherical dendritic organic silicon macromolecule serves as a cross-linking compensation point and is applied to a solvent-free polysiloxane compound SL. The two-step circulation method includes hydrosilylation and nucleophilic substitution. Active sites capable of diverging are led into annular siloxane in the hydrosilylation. The nucleophilic substitution aims to lead in more cross-linking reaction sites and ensure that the solvent-free polysiloxane compound obtains a curing coating with a perfect cross-linking network structure when cured on a sheet substrate, so that stable performance of an anti-adhesion coating is ensured.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of spherical dendritic silicone macromolecule and preparation method thereof and application.
Background technology
Anti-adhesive silicone coating refers to the substrate being coated with one deck antiadhesion barrier on the surface, and it can make the very strong material of cementability peel away easily.Wherein play chemical that is antiseized, buffer action and be called separant.Organosilicon Release Agent because its toxicity is little, surface tension is 20 ~ 24mN/m, good with paper wettability, easily paper surface formed firmly film, temperature applicable range wide, to advantages such as binder migration are little, be current most widely used separant.Organosilicon is as paper release agent, mechanism of action is that methyl can rotate freely at substrate surface, thus its orderly at substrate surface, intensive arrangement can be made, effectively can prevent tackiness agent molecule or the basad infiltration of segment, and the polarity of methyl own is very little, volume is very little, surface tension is low, can lower-surface-free-energy surface be formed after coating, less to tackiness agent reactive force, thus there is good stripping performance.Therefore, the organosilicon macromolecule layer forming the cross-linked network system structure of one deck densification at paper surface can prevent tackiness agent from penetrating in tight zone.There is antiadhesion barrier that is antiseized, isolation features and be mainly used for the productions such as self adhesive label's paper, pressure-sensitive gummed paper, finishing material compound interleaving paper, imitation leather separate-type paper and medical diagnosis equipment interleaving paper, make the substrate after process have antiseized, isolation performance.
Organic silicon type separant, can be divided into according to physical aspect aspect: solvent-borne type, emulsion-type and no-solvent type three class.From current development trend, solvent-borne type have be easy to preparation, easy to use, the advantages such as production environment is less demanding; But having the shortcomings such as inflammable, unfavorable health, contaminate environment, the condensation cured release agent of solvent-borne type, because of environmental pollution, to be harmful to health and safety problem is generally limited use.The advantage of emulsion-type is then operational safety, and free from environmental pollution, function is extensive, and its shortcoming makes greatly and easily curl etc. for dry power consumption, and be restricted owing to using solvent-borne type and the fast development of film based packaging material, potentiality of its development are still huge.The feature of no-solvent type is then solidification quick, energy-conservation, safety, nonpollution environment.At present along with the maturation of five roller coating techniques, under the condition of high-speed coating, low glue spread and even spread can be ensured, the development fast that solvent-free organic silicon parting agent obtains.Add-on type, condensed type, irradiation type can be divided into according to crosslinking reaction during its last film.Compare from aspects such as the operability that state of cure, stripping performance, anti-stick property, coating formulation design, add-on type is better than condensed type.Along with the raising that China is realized green economy, solvent type silicone release agent is progressively substituted.
From the patent reported at present, prepare a kind of material giving the antiseized character of viscous substance.This material mainly by curable silicone composition is coated on as paper, laminated paper, synthetic resin film and tinsel and so on flat substrates on the surface, then under the catalyzer existent condition of platinum class, thermofixation obtains one deck coating.This silicone composition main ingredient is organopolysiloxane and the organic hydrogen polysiloxanes with alkenyl.Such as, Chinese patent application publication number CN1335344A discloses a kind of silicone composition, and said composition contains the low viscous organopolysiloxane with hexenyl, poly-organohydrogensiloxanes and platinum class catalyzer.Wherein comprise two kinds in organic hydrogen polysiloxanes, a kind of is the hydrogeneous poly-organohydrogensiloxanes of end, and a kind of is the hydrogeneous poly-organohydrogensiloxanes of side chain.Under the object of this patent mainly ensures the condition controlled at certain peeling rate, stable off-type force can be obtained and ensure that the film of solidification has good remaining tackiness for viscous substance.In actual production, before separate paper or antiadhesion barrier rolling, be coated with solidified coating with viscous substance, solidified coating can contact with metal or plastic foil or plastic roller, cause solidified coating to be damaged, thus cause the sliding of solidified coating difference and rolling can not be completed smoothly.Wherein JP61-159480A and JP61-264052A discloses a kind of solvent-free addition reaction solidified nature organopolysiloxane composition, in the composition, except adopt there is alkenyl organopolysiloxane and organic hydrogen polysiloxanes except, additionally use composition based on linear organopolysiloxane that molecular end has a hydroxyl.Although make moderate progress to a certain extent, still there is no gratifying sliding.Chinese patent application publication number CN101616995A is in order to solve this problem of sliding, propose a kind of organopolysiloxane composition, wherein a kind of host adopts the organosiloxane compound of hyper-branched point, by adopting the organopolysiloxane of this design, well solve the problem of sliding.
In the patent reported at present, mainly for solution and the remnants adhesion rate problem generally all paid close attention to of off-type force, sliding and the sassafras coefficient that rubs.But solvent-free poly-organosiloxane compositions is as in release agent, ubiquity the high problem of aging off-type force, so in use, aging off-type force raises, the problem that in use product can not tear open can be caused, the use properties of product can be affected like this, this problem is mainly due under the condition of high temperature and high speed, the polymethyl hydrogen siloxane of part is had to have little time reaction, reaction system is completely not crosslinked, deposit in process in follow-up, the silicon hydrogen that the silicon hydrogen that result in polymethyl hydrogen siloxane there occurs in crosslinking phenomena and polymethyl hydrogen siloxane contacts in a large number with water vapor in air, there is further hydrolysis-condensation reaction, result in the increase of cross-linking density, the increase of cross-linking density result in the rising of aging off-type force.In order to address this problem, we will improve under the condition of high temperature and high speed, and the silicon H-H reaction in polymethyl hydrogen siloxane is complete, and like this in follow-up depositing, off-type force can remain stable.At present, all adopt the active group generation crosslinking reaction between linear polysiloxane in most document, under the condition of high temperature and high speed, collision probability between active group between linear polysiloxane can be smaller, and the silicon hydrogen which results in a large amount of polymethyl hydrogen siloxanes does not participate in reaction.
Summary of the invention
In order to overcome the deficiencies in the prior art and shortcoming, primary and foremost purpose of the present invention is to provide a kind of spherical dendritic silicone macromolecule.
Another object of the present invention is to the preparation method that above-mentioned spherical dendritic silicone macromolecule is provided.
Another object of the present invention is the application providing above-mentioned spherical dendritic silicone macromolecule.
4th object of the present invention is to provide a kind of solvent-free poly-organopolysiloxane mixture, the number of the cross-link bond in the unit volume in raising system is carried out in the organopolysiloxane mixture of the anti-stick coating that this mixture has many reaction site spherical dendritic macromole by introducing edge solidifies to solvent-free formation, obtain stable off-type force, reduce the consumption of poly-organohydrogensiloxanes, the rising of aging off-type force under reduction room temperature storage condition.
Object of the present invention is achieved through the following technical solutions:
A kind of spherical dendritic silicone macromolecule, its structural formula is such as formula shown in I:
Wherein, described R
1for monovalent hydrocarbon;
Described R
2for having the alkenyl of reactive behavior;
Described R
3be preferably fluorine, chlorine, bromine or iodine;
Described R
4for end has alcohol compound or the carboxylic acid compound of alkenyl group;
N be spherical dendritic silicone macromolecule disperse growth indices, n is the positive integer of 0 ~ 5000; The span of n is preferably 1 ~ 10;
The preparation method of described spherical dendritic silicone macromolecule, comprises following steps:
(1) by Compound D
0be dissolved in solvent B, under the effect of catalyzer C, by addition reaction of silicon with hydrogen by Compound D as the base core molecule of spherical dendritic silicone macromolecule and compd A
0edge carry out dispersing process and obtain Compound D
1X; By Compound D
1Xbe dissolved in solvent F with compd E, under the condition of basic catalyst G catalysis, carry out nucleophilic substitution reaction, and then pass through two one-step circulation methods of an addition reaction of silicon with hydrogen and nucleophilic substitution reaction, obtain the Compound D of alkenylation
1, be the spherical dendritic silicone macromolecule of n=1;
(2) Compound D for preparing of step (1)
1be dissolved in solvent B, under the effect of catalyzer C, by addition reaction of silicon with hydrogen by Compound D as the base core molecule of spherical dendritic silicone macromolecule and compd A
1edge carry out dispersing process and obtain Compound D
2X; By Compound D
2Xbe dissolved in solvent F with compd E, under the condition of basic catalyst G catalysis, carry out nucleophilic substitution reaction; And then on the basis of step (1), by two one-step circulation methods of an addition reaction of silicon with hydrogen and nucleophilic substitution reaction, obtain the Compound D of alkenylation
2, be the spherical dendritic silicone macromolecule of n=2;
(3) step (1) and step (2) are a circulation of the dendritic silicone macromolecule of synthesizing spherical respectively, as shown in step (1) and (2), the product of an above circulation nucleophilic substitution reaction, as the base core molecule circulating reaction of spherical dendritic silicone macromolecule, obtains the Compound D of alkenylation
n, be the spherical dendritic silicone macromolecule of n≤3;
Compound D described in step (1)
0the structural formula of (the siloxanes tetramer) is such as formula shown in II:
Described R
1for monovalent hydrocarbon; Described R
2for having the alkenyl of reactive behavior;
Described R
1be preferably alkyl (methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl or decyl etc.), aryl (phenyl, tolyl or xylyl etc.) or aralkyl (phenmethyl or styroyl etc.); R
1more preferably methyl;
Described R
2be preferably vinyl, propenyl, butenyl, 5-hexenyl, octenyl or decene base; Described R
2more preferably vinyl;
Described D
0viscosity 25 DEG C time is 30 ~ 500 milli handkerchiefs
.second; Described D
0preferably 25 DEG C time, viscosity is 50 ~ 250 milli handkerchiefs
.second;
The structural formula of the compd A described in step (1) is H
xr
5 ysiR
3 z; Described R
5for the organic group monovalent hydrocarbon with silicon bonding; Described R
3for having the halogen group of reactive behavior;
Wherein, the number of H is x, and x=1; R
5number be y, and y=0 ~ 3; R
3number be z, and z=1 ~ 3; X, y, z three sum is 4;
Described R
5be preferably alkyl (methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl or decyl etc.), aryl (phenyl, tolyl or xylyl etc.) or aralkyl (phenmethyl or styroyl etc.); Described R
5more preferably methyl;
Described R
3be preferably fluorine, chlorine, bromine or iodine; Described R
3more preferably wherein preferred chlorine; As required, select the compd A with the halogen atom of different number can obtain the spherical dendritic macromole of different divergent state, there is if select the compd A of three halogens, then the index with three is doubly dispersed by spherical dendritic macromole, have the compd A of two halogens if select, then the index with two is doubly dispersed by spherical dendritic macromole;
Compound D described in step (1)
0be 1:(4 ~ 6 with the mol ratio of compd A), to ensure tetramer Compound D
0in reactive behavior point can fully react; Compound D described in step (1)
01:(4 ~ 5 are preferably) with the mol ratio of compd A;
The state of compd A described in step (1) 25 DEG C time is preferably liquid;
Solvent B described in step (1) is at least one in pimelinketone, tetrahydrofuran (THF), acetone, butanone, toluene, methylene dichloride, trichloromethane, ether, sherwood oil, is preferably tetrahydrofuran (THF);
Catalyzer C described in step (1) is at least one in Platinic chloride, hydrochloro-auric acid, Karst (karstedt) catalyzer and platinum C catalyst;
The consumption of the catalyzer C described in step (1) is with Compound D
0in the molar weight of reaction active groups determine, be Compound D
01 × 10 of the molar weight of alkenyl groups
-3~ 1 × 10
-6;
The reaction conditions of the addition reaction of silicon with hydrogen described in step (1) is: stirring reaction 24 ~ 72h under room temperature (20 ~ 35 DEG C) condition;
After addition reaction of silicon with hydrogen described in step (1) completes, also comprise following purification step: extract lower boiling material by decompression, precipitated in pentane by the mixture obtained, and then catalyzer can be removed; Finally by centrifugal purification product, and extract lower boiling solvent, obtain colorless oil as product D
1X;
Compound D described in step (1)
1Xstructural formula such as formula shown in III:
Wherein, described R
1for monovalent hydrocarbon; Described R
2for having the alkenyl of reactive behavior; Described R
3be preferably fluorine, chlorine, bromine or iodine;
The structural formula of the compd E described in step (1) is R
4-OH;
Wherein, R
4alcohol compound or the carboxylic acid compound that end has alkenyl group;
Described R
4be preferably vinylcarbinol, propiolic alcohol, 3-butenol, 4-pentenol, 5-hexenol, 6-heptenol, 7-octenol, 8-nonenol or 9-decenol, vinylformic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octylenic acid, 8-nonenoic acid or 9-decylenic acid; More preferably vinylcarbinol or vinylformic acid; Alcoholic extract hydroxyl group wherein or hydroxy-acid group are mainly in order to the halogen group introduced in follow-up and the first step reacts;
Solvent F described in step (1) is at least one in pimelinketone, tetrahydrofuran (THF), acetone, butanone, toluene, methylene dichloride, trichloromethane, ether and sherwood oil; Be preferably toluene;
Basic catalyst G described in step (1) is N, N-dimethylcyclohexylamine, two (2-dimethylaminoethyl) ether, N, N, N', N'-tetramethyl-Alkylenediamine, triethylamine, N, N-dimethyl benzylamine, solid amine, N-ethylmorpholine, N-methylmorpholine (NMM), N, N '-diethyl piperazine, trolamine, Tetramethyl Ethylene Diamine (DMEA), pyridine or N, N '-dimethyl pyridine; Be preferably Tetramethyl Ethylene Diamine (DMEA);
The concrete operations of the nucleophilic substitution reaction described in step (1) are: by catalyzer G and Compound D
1Xbe dissolved in solvent F, obtain solvent system 1; Then compd E is dissolved in F, obtains solvent system 2; Be added drop-wise to by solvent system 2 in solvent system 1, rate of addition controls at 50 ~ 1000 μ L/min; After being added dropwise to complete, temperature of reaction system is elevated to 40 ~ 80 DEG C, continues reaction 1 ~ 5h, after reaction terminates, carry out precipitation with pentane and remove amine salt, the product obtained extracts lower boiling material by decompression, last product passed through silicagel column and carried out purifying, finally obtained colourless oil liquid D
1;
The described application of spherical dendritic silicone macromolecule in antiseized field;
Described spherical dendritic silicone macromolecule can be applied to the solvent-free poly-organopolysiloxane mixture of preparation, make solvent-free poly-organopolysiloxane mixture in the substrate being cured to sheet-form, obtain the perfect solidified coating of cross-linked network structure, thus ensure that the stable performance of anti-stick coating;
A kind of solvent-free poly-organopolysiloxane mixture, comprises above-mentioned spherical dendritic silicone macromolecule;
Described solvent-free poly-organopolysiloxane mixture, preferably comprises as follows by the component of mass parts:
Spherical dendritic silicone macromolecule;
The content of described spherical dendritic silicone macromolecule is the spherical dendritic silicone macromolecule that every 100 mass parts alkenyls gather containing 0.1 ~ 10 weight part in the mixture of organopolysiloxane, polymethyl hydrogen siloxane, catalyzer and inhibitor;
Described alkenyl gathers can at the two ends of organopolysiloxane and branched positional place with two of silicon bonding and above kiki alkenyl group in organopolysiloxane;
Described alkenyl gathers organopolysiloxane and is preferably that vinyl gathers organopolysiloxane, propenyl gathers organopolysiloxane, butenyl gathers organopolysiloxane, 5-hexenyl gathers organopolysiloxane, octenyl gathers organopolysiloxane and decene base gathers at least one in organopolysiloxane; More preferably 5-hexenyl gathers organopolysiloxane or vinyl gathers organopolysiloxane;
Can at the two ends of organopolysiloxane and branched positional place with two of silicon bonding and above hydrogen atom in described polymethyl hydrogen siloxane;
Described catalyzer is the catalyzer of the VIII for forming cross linking membrane under hot conditions fast, is preferably the complex compound of platinum or the complex compound of rhodium of organic active; The more preferably complex compound of organic active platinum;
Described inhibitor is the inhibitor that can prevent gelling and solidification from realizing Quick cross-linking solidification under the maximization in bath life-span and condition at high temperature and high speed in the temperature range of regulation; Described regulation temperature range be 20 ~ 60 DEG C, bath life-span 8 ~ 24h, the scope of high temperature is 100 ~ 200 DEG C, and scope is at a high speed 50 ~ 1000m/min;
Described inhibitor is preferably at least one in alkynol compound, enyne compounds, organic nitrogen compound, organo phosphorous compounds and anhydrides compound;
The alkynol compound of suitable boiling point class is selected according to the temperature of solidifying and speed, described alkynol compound is preferably 3-methyl isophthalic acid-butine-ol, 3,5-dimethyl-1-hexin-3-alcohol, 3-methyl isophthalic acid-hexin-3-alkene or 1-ethynyl-1-hexalin; Described anhydrides compound is preferably dimethyl maleate or dimethyl fumarate;
According to the few principle preferentially of amount, described inhibitor is 1-ethynyl-1-hexalin more preferably;
Described alkenyl gathers the mol ratio of organopolysiloxane and polymethyl hydrogen siloxane for (1.0:0.5) ~ (1.0:5.0), wherein, is preferably (1.0:1.0) ~ (1.0:2.5);
The content of described spherical dendritic silicone macromolecule is preferably every 100 mass parts alkenyls and gathers the spherical dendritic silicone macromolecule containing 0.5 ~ 5 weight part in the mixture of organopolysiloxane, polymethyl hydrogen siloxane, catalyzer and inhibitor; If obtain the anti-stick coating of high off-type force, then the consumption of spherical dendritic macromole is higher, if will obtain the anti-stick coating of low off-type force, then the consumption of spherical dendritic macromole is on the low side;
The preparation method of described solvent-free poly-organopolysiloxane mixture, comprise following steps: alkenyl is gathered organopolysiloxane, polymethyl hydrogen siloxane, catalyzer, inhibitor and spherical dendritic silicone macromolecule and mix, namely obtain solvent-free poly-organopolysiloxane mixture;
Described solvent-free poly-organopolysiloxane mixture is applied on the various base materials as the paper of paper, laminated polyolefin, synthetic resin film, enamelled paper and tinsel and so on, then carry out hot setting, this mixture defines the strippable anti-stick coating of viscous substance from substrate surface.
Principle of the present invention: carry out the dendritic silicone macromolecule of synthesizing spherical by two one-step circulation methods in the present invention, wherein two one-step circulation methods comprise: addition reaction of silicon with hydrogen and nucleophilic substitution reaction.Addition reaction of silicon with hydrogen is in annular siloxane, introduce the avtive spot that can carry out dispersing, and the object of nucleophilic substitution reaction introduces more crosslinking reaction site.Wherein, Compound D
0(the siloxanes tetramer) is the base core molecule in the present invention, component D
0a base core is provided for building spherical dendritic macromole further; Step (1) and (2) are a circulation of two one-step circulation method synthesizing spherical dendritic macromoles respectively.By once circulating of step (1) the reactive behavior site at the edge of four polycyclic body compounds dispersed, from D
0obtain D
1the increase number of edge response avtive spot depends on the number of halogen atom in compd A, according to the spherical dendritic macromole selecting the compound with the halogen atom of different number can obtain different divergent state, there is if select the compound of three halogens, then the index with three is doubly dispersed by spherical dendritic macromole, have the compound of two halogens if select, then the index with two is doubly dispersed by spherical dendritic macromole.
Next by Compound D
1be dissolved in solvent B with compd A, under the effect of catalyzer C, by Si―H addition reaction by Compound D
1the edge carried out carries out dispersing process and obtains Compound D
2X; Second step is by Compound D
2Xbe dissolved in solvent F with compd E, under basic catalyst G condition, carry out the Compound D that nucleophilic substitution reaction obtains alkenylation
2, thus the spherical dendritic macromole D that edge has more reaction site can be obtained
2.By that analogy and circulation, the compound synthesizing certain number reaction site can be carried out according to actual needs.
The present invention has following advantage and effect relative to prior art:
(1) the adding of spherical dendroid silicone macromolecule, the cross-linked network structure that solvent-free poly-organopolysiloxane mixture is formed is more perfect, obtains the poly organic silicon anti-stick coating that off-type force is more stable.
(2) the reactive behavior site of dispersing in spherical dendroid silicone macromolecule can ensure that the Si-H in solvent-free poly-organopolysiloxane mixture in polymethyl hydrogen siloxane reacts completely, thus ensure under room temperature storage condition, stablizing of aging off-type force.
(3) the adding of spherical dendroid silicone macromolecule, the consumption of polymethyl hydrogen siloxane in solvent-free poly-organopolysiloxane can be reduced to a certain extent, thus the possibility fundamentally reducing off-type force and raise under room temperature storage condition.
(4) spherical dendroid silicone macromolecule can improve solvent-free poly-organopolysiloxane mixture to a certain extent and is being cured to the suprabasil remaining adhesion rate of sheet-form, thus ensures that poly-organopolysiloxane can not move in follow-up use procedure.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Under all situations, part all represents weight, and ppm represents weight, and unit is mg/kg; In addition, at 25 DEG C by described method tested viscosity.In addition, by the effect adopting the test Tesa7475 adhesive tape of standard to carry out the solidification testing the solvent-free poly-organopolysiloxane coating of adding spherical dendritic macromole, be used as by test off-type force, aging off-type force, remaining adhesion rate three indexs the performance index evaluating product.Testing method is summarized as follows:
The mensuration of off-type force: adopt load cell type peeling force trier, draw speed is 30cm/min, stretching distance 100mm, specimen size 200 × 25mm.Testing method: commercially available pressure-sensitive Tesa7475 adhesive tape is glued note to the offset paper surface scribbling separant (cured film), attention can not produce air gap (with the roll extrusion three times back and forth of 2kg pressure roller) and then carry out 180 ° of peel tests in inside.
The mensuration of aging off-type force: adopt load cell type peeling force trier, draw speed is 30cm/min, stretching distance 100mm, specimen size 200 × 25mm.Testing method: commercially available pressure-sensitive Tesa7475 adhesive tape is glued note to the offset paper surface scribbling separant (cured film), attention can not produce air gap (with the roll extrusion three times back and forth of 2kg pressure roller) in inside, then relative humidity 80% is put in, aging 24h under the condition of 60 DEG C.Then 180 ° of peel tests are carried out.
The mensuration of remaining clinging power: remaining adhesive power measures because organosilicon moves the reduction causing adhesive power.Standard Tesa7475 adhesive tape after measuring peeling force is sticked on on-gauge plate, with the roll extrusion 3 times back and forth of 2kg pressure, room temperature 20 DEG C, under the state of relative humidity 65%, place 3h, re-use load cell type electronic stripping tester and carry out 180 ° of strippings with the speed of 30cm/min, survey the size that numerical value is residual adhesive power.
Embodiment 1
(1) by 5.14g tetravinyl cyclotetrasiloxane (D
0) (t etram-ethyltetravinylcyclotetrasiloxane, R
1methyl, R
2vinyl), 7.09g dimethyl dichlorosilane (DMCS) (A) and 0.1g Karstedt catalyzer (C) be dissolved in 300mL tetrahydrofuran (THF) (B) and mix, wherein the consumption of Karstedt catalyzer is calculated by the molar weight of tetravinyl cyclotetrasiloxane medium vinyl, and the molar weight of platinum is 1 × 10 of vinyl
-4.Under normal temperature condition, react 24h, pass through
1h-NMR monitors reaction.Excessive unreacted dimethyl dichlorosilane (DMCS) and solvent are removed by decompression rotatory evaporator.Sink catalyzer by pentane, removing lower boiling material finally by vacuumizing, obtaining colourless oil liquid 11.0g (D
1X), productive rate 90%; The product D obtained
1Xedge contain 8 active group Cl, for follow-up reaction is laid a good groundwork;
(2) by the D of 11.0g
1Xbe dissolved in the toluene of 150mL with the Tetramethyl Ethylene Diamine (TMED) of 12.71g, obtain solvent system 1; The vinylcarbinol (E) of 6.35g is dissolved in solvent 50mL toluene (F), obtains solvent system 2; Be added drop-wise in solvent system 1 by solvent system 2 while stirring, rate of addition is 100 μ L/min.After being added dropwise to complete, temperature of reaction is elevated to 50 DEG C, continues reaction 2h; Pass through
1h-NMR monitors reaction.Precipitated by pentane and dispose amine salt.Then lower boiling liquid is extracted by vacuum decompression.The product obtained passed through silicagel column and carried out purification process.Obtain product D
1 211.3g, productive rate is 65%.
(3) D
1 2continue according to two one-step circulation methods down to synthesize the spherical dendritic macromole that can obtain containing 16,32,64,128 reactive behavior sites in edge.Be numbered D respectively
2 2, D
3 2, D
4 2, D
5 2.Wherein subscript refers to the rising tendency of spherical dendritic macromole, doubly increases with the index of 2.Subscript 2,3,4,5 be respectively refer to the s-generation, the third generation, forth generation, the 5th generation spherical dendritic macromole.
Embodiment 2
(1) by 5.14g tetravinyl cyclotetrasiloxane (D
0) (t etram-ethyltetravinylcyclotetrasiloxane, R
1methyl, R
2vinyl), 8.07g trichlorosilane (A) and 0.1g Karstedt catalyzer (C) be dissolved in 300mL tetrahydrofuran (THF) (B) and mix, wherein the consumption of Karstedt catalyzer is calculated by the molar weight of tetravinyl cyclotetrasiloxane medium vinyl, and the molar weight of platinum is 1 × 10 of vinyl
-4.Under normal temperature condition, react 24h, pass through
1h-NMR monitors reaction.Excessive unreacted trichlorosilane and solvent are removed by decompression rotatory evaporator.Sink catalyzer by pentane, removing lower boiling material finally by vacuumizing, obtaining colourless oil liquid 11.9g (D
1X), productive rate 90%, the product D obtained
1Xedge just contain 12 active group Cl, for follow-up reaction is laid a good groundwork;
(2) by the D of 11.9g
1Xbe dissolved in the toluene of 250mL with the Tetramethyl Ethylene Diamine (TMED) of 20.61g, obtain solvent system 1; The vinylcarbinol (E) of 10.31g is dissolved in solvent 100mL toluene (F), obtains solvent system 2; Be added drop-wise in solvent system 1 by solvent system 2 while stirring, rate of addition is 100 μ L/min.After being added dropwise to complete, temperature of reaction is elevated to 50 DEG C, continues reaction 2h.Pass through
1h-NMR monitors reaction.Precipitated by pentane and dispose amine salt.Then lower boiling liquid is extracted by vacuum decompression.The product obtained passed through silicagel column and carried out purification process.Obtain product D
1 313.33g, productive rate is 60%.
(3) D
1 3continue according to two one-step circulation methods down to synthesize the spherical dendritic macromole that can obtain containing 36,108 reactive behavior sites in edge.Be numbered D respectively
2 3, D
3 3.Wherein subscript refers to the rising tendency of spherical dendritic macromole, doubly increases with the index of 3, and subscript 2,3 is refer to the s-generation, the spherical dendritic macromole of the third generation respectively.
Embodiment 3
(1) by 5.14g tetravinyl cyclotetrasiloxane (D
0) (t etram-ethyltetravinylcyclotetrasiloxane, R
1methyl, R
2vinyl), 7.09g dimethyl dichlorosilane (DMCS) (A) and 0.1g Karstedt catalyzer (C) be dissolved in 300mL tetrahydrofuran (THF) (B) and mix, wherein the consumption of Karstedt catalyzer is calculated by the molar weight of tetravinyl cyclotetrasiloxane medium vinyl, and the molar weight of platinum is 1 × 10 of vinyl
-3.Under normal temperature condition, react 72h, pass through
1h-NMR monitors reaction.Excessive unreacted dimethyl dichlorosilane (DMCS) and solvent are removed by decompression rotatory evaporator.Sink catalyzer by pentane, removing lower boiling material finally by vacuumizing, obtaining colourless oil liquid 11.0g (D
1X), productive rate 90%; The product D obtained
1Xedge contain 8 active group Cl, for follow-up reaction is laid a good groundwork;
(2) by the D of 11.0g
1Xbe dissolved in the toluene of 150mL with the Tetramethyl Ethylene Diamine (TMED) of 12.71g, obtain solvent system 1; The vinylcarbinol (E) of 6.35g is dissolved in solvent 50mL toluene (F), obtains solvent system 2; Be added drop-wise in solvent system 1 by solvent system 2 while stirring, rate of addition is 1000 μ L/min.After being added dropwise to complete, temperature of reaction is elevated to 80 DEG C, continues reaction 1h; Pass through
1h-NMR monitors reaction.Precipitated by pentane and dispose amine salt.Then lower boiling liquid is extracted by vacuum decompression.The product obtained passed through silicagel column and carried out purification process.Obtain product D
1 212g, productive rate is 69%.
Embodiment 4
(1) by 5.14g tetravinyl cyclotetrasiloxane (D
0) (t etram-ethyltetravinylcyclotetrasiloxane, R
1methyl, R
2vinyl), 7.09g dimethyl dichlorosilane (DMCS) (A) and 0.1g Karstedt catalyzer (C) be dissolved in 300mL tetrahydrofuran (THF) (B) and mix, wherein the consumption of Karstedt catalyzer is calculated by the molar weight of tetravinyl cyclotetrasiloxane medium vinyl, and the molar weight of platinum is 1 × 10 of vinyl
-6.Under normal temperature condition, react 48h, pass through
1h-NMR monitors reaction.Excessive unreacted dimethyl dichlorosilane (DMCS) and solvent are removed by decompression rotatory evaporator.Sink catalyzer by pentane, removing lower boiling material finally by vacuumizing, obtaining colourless oil liquid 11.0g (D
1X), productive rate 90%; The product D obtained
1Xedge just contain 8 active group Cl, for follow-up reaction is laid a good groundwork.
(2) by the D of 11.0g
1Xbe dissolved in the toluene of 150mL with the Tetramethyl Ethylene Diamine (TMED) of 12.71g, obtain solvent system 1; The vinylcarbinol (E) of 6.35g is dissolved in solvent 50mL toluene (F), obtains solvent system 2; Be added drop-wise in solvent system 1 by solvent system 2 while stirring, rate of addition is 50 μ L/min.After being added dropwise to complete, temperature of reaction is elevated to 40 DEG C, continues reaction 5h; Pass through
1h-NMR monitors reaction.Precipitated by pentane and dispose amine salt.Then lower boiling liquid is extracted by vacuum decompression.The product obtained passed through silicagel column and carried out purification process.Obtain product D
1 210.5g, productive rate is 60%.
The effect of spherical dendritic macromole in solvent-free poly-organopolysiloxane mixture that embodiment 5 is different
(1) by the methyl vinyl silicone of 100 parts, (dimethylvinyl siloxane end-blocking is all used at its molecule two ends, and viscosity is 100mPa
.s), (trimethicone end-blocking is all used at its molecule two ends to the polymethyl hydrogen siloxane of 7.5 parts, viscosity is 30mPa.s), 0.05 part of 1-ethynyl-1-hexalin mixes, then in mixture, adding the Karstedt catalyzer of 8ppm (2.7 mass parts), (wherein the content of platinum is 0.3%, the structure of Karstedt catalyzer is 1, 3-divinyl-1, 1, 3, the complex compound of 3-tetramethyl disiloxane and platinum), thus form solvent-free poly-organopolysiloxane mixture SL (control group 1), then the Ge Laxin paper this mixture being coated onto polyethylene particle film solidifies,
(2) solvent-free poly-organopolysiloxane mixture SL is prepared according to the method for step (1), then by embodiment 1 with 2-in-1 become the spherical dendritic macromole of difference to add in solvent-free poly-organopolysiloxane mixture SL system and to mix, then film-forming is distinguished on the Ge Laxin paper of polyethylene particle film, wherein, the interpolation kind of spherical dendritic macromole and content in table 1, totally 7 treatment group (treatment group 2 ~ 8).Test off-type force, aging off-type force, the remaining adhesion rate of the separate-type paper obtained.
The interpolation kind of spherical dendritic macromole in table 1 treatment group 2 ~ 8
(3) the spherical dendritic macromole of different additions is probed on the impact of the solidification effect of solvent-free poly-organopolysiloxane mixture: prepare solvent-free poly-organopolysiloxane mixture SL according to the method for step (1), by embodiment 1 with 2-in-1 become the spherical dendritic macromole of difference add in solvent-free poly-organopolysiloxane mixture SL system and mix, then film-forming is distinguished on the Ge Laxin paper of polyethylene particle film, wherein, the interpolation kind of spherical dendritic macromole and content are in table 1, totally 6 treatment group (treatment group 9 ~ 14).Test off-type force, aging off-type force, the remaining adhesion rate of the separate-type paper obtained.
The interpolation consumption of spherical dendritic macromole in table 2 treatment group 9 ~ 14
(4) under the condition of high temperature and high speed, polymethyl hydrogen siloxane can not alkenyl generation crosslinking reaction completely and in system, deposits in process like this in follow-up, polymethyl hydrogen siloxane can and the middle moisture generation crosslinking reaction of environment.The present invention is by introducing spherical dendritic macromole, and the cross-link bond in unit volume can increase, and so just can ensure the silicon hydrogen reaction as much as possible in polymethyl siloxane.The rising of aging off-type force under reduction room temperature storage condition.
Prepare solvent-free poly-organopolysiloxane mixture SL according to the method for step (1), wherein the interpolation content of polymethyl hydrogen siloxane is in table 3, and other Feedstock Component content remain unchanged; Then spherical for third generation dendritic macromole to be added in solvent-free poly-organopolysiloxane mixture SL system and to mix, film-forming is on the Ge Laxin paper of polyethylene particle film respectively, wherein, the interpolation content of spherical dendritic macromole is 2% of the total amount of solvent-free poly-organopolysiloxane SL, in table 3, totally 2 treatment group (treatment group 15,16).
The interpolation content of table 3 treatment group 15,16 polymethyl hydrogen siloxane
The Performance comparision of the solvent-free poly-organopolysiloxane mixture that table 4 control group 1 and treatment group 2 ~ 16 prepare
Table 4 is the Performance comparision of the solvent-free poly-organopolysiloxane mixture that 16 treatment group finally prepare.From group 1 and 2,3,4,5 and group 2,6,7,8 relatively, add spherical dendroid silicone macromolecule in solvent-free poly-organosiloxane compositions, off-type force can slightly raise.But from group 8, when containing too much reactive behavior site in spherical dendritic macromole, the generation of the sub-crosslinking phenomena in reactive behavior site can be caused, thus cause the raw abnormal of off-type force to raise.From group 5 and 9,10,11 and group 7 and 12,13,14 relatively, we can draw, the addition of spherical dendroid silicone macromolecule is 1 ~ 2%, and too much addition also can cause the generation of the phenomenon of the self-crosslinking in the reactive behavior site of spherical dendroid silicone macromolecule.From the Data Comparison of group 9 and 15,16, we can draw, under the addition of spherical dendroid silicone macromolecule is the condition of 2%, suitably reduces the amount of polymethyl hydrogen siloxane, can well ensure the stability of off-type force.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a spherical dendritic silicone macromolecule, is characterized in that its structural formula is such as formula shown in I:
Wherein, described R
1for monovalent hydrocarbon;
Described R
2for having the alkenyl of reactive behavior;
Described R
3for fluorine, chlorine, bromine or iodine;
Described R
4for end has alcohol compound or the carboxylic acid compound of alkenyl group;
N be spherical dendritic silicone macromolecule disperse growth indices.
2. the preparation method of spherical dendritic silicone macromolecule according to claim 1, is characterized in that comprising following steps:
(1) by Compound D
0be dissolved in solvent B, under the effect of catalyzer C, by addition reaction of silicon with hydrogen by Compound D as the base core molecule of spherical dendritic silicone macromolecule and compd A
0edge carry out dispersing process and obtain Compound D
1X; By Compound D
1Xbe dissolved in solvent F with compd E, under the condition of basic catalyst G catalysis, carry out nucleophilic substitution reaction, and then pass through two one-step circulation methods of an addition reaction of silicon with hydrogen and nucleophilic substitution reaction, obtain the Compound D of alkenylation
1, be the spherical dendritic silicone macromolecule of n=1;
(2) Compound D for preparing of step (1)
1be dissolved in solvent B, under the effect of catalyzer C, by addition reaction of silicon with hydrogen by Compound D as the base core molecule of spherical dendritic silicone macromolecule and compd A
1edge carry out dispersing process and obtain Compound D
2X; By Compound D
2Xbe dissolved in solvent F with compd E, under the condition of basic catalyst G catalysis, carry out nucleophilic substitution reaction; And then on the basis of step (1), by two one-step circulation methods of an addition reaction of silicon with hydrogen and nucleophilic substitution reaction, obtain the Compound D of alkenylation
2, be the spherical dendritic silicone macromolecule of n=2;
(3) step (1) and step (2) are a circulation of the dendritic silicone macromolecule of synthesizing spherical respectively, as shown in step (1) and (2), the product of an above circulation nucleophilic substitution reaction, as the base core molecule circulating reaction of spherical dendritic silicone macromolecule, obtains the Compound D of alkenylation
n, be the spherical dendritic silicone macromolecule of n≤3;
Compound D described in step (1)
0structural formula such as formula shown in II:
Described R
1for monovalent hydrocarbon; Described R
2for having the alkenyl of reactive behavior;
The structural formula of the compd A described in step (1) is H
xr
5 ysiR
3 z; Described R
5for the organic group monovalent hydrocarbon with silicon bonding; Described R
3for having the halogen group of reactive behavior; Wherein, the number of H is x, and x=1; R
5number be y, and y=0 ~ 3; R
3number be z, and z=1 ~ 3; X, y, z three sum is 4;
Solvent B described in step (1) is at least one in pimelinketone, tetrahydrofuran (THF), acetone, butanone, toluene, methylene dichloride, trichloromethane, ether, sherwood oil;
Catalyzer C described in step (1) is at least one in Platinic chloride, hydrochloro-auric acid, Karst catalyzer and platinum C catalyst;
The structural formula of the compd E described in step (1) is R
4-OH; Wherein, R
4alcohol compound or the carboxylic acid compound that end has alkenyl group;
Solvent F described in step (1) is at least one in pimelinketone, tetrahydrofuran (THF), acetone, butanone, toluene, methylene dichloride, trichloromethane, ether and sherwood oil;
Basic catalyst G described in step (1) is N, N-dimethylcyclohexylamine, two (2-dimethylaminoethyl) ether, N, N, N', N'-tetramethyl-Alkylenediamine, triethylamine, N, N-dimethyl benzylamine, solid amine, N-ethylmorpholine, N-methylmorpholine, N, N '-diethyl piperazine, trolamine, Tetramethyl Ethylene Diamine, pyridine or N, N '-dimethyl pyridine.
3. the preparation method of spherical dendritic silicone macromolecule according to claim 1, is characterized in that:
Compound D described in step (1)
0be 1:(4 ~ 6 with the mol ratio of compd A).
4. the preparation method of spherical dendritic silicone macromolecule according to claim 1, is characterized in that:
The reaction conditions of the addition reaction of silicon with hydrogen described in step (1) is: stirring reaction 24 ~ 72h under room temperature condition.
5. the preparation method of spherical dendritic silicone macromolecule according to claim 1, is characterized in that:
The concrete operations of the nucleophilic substitution reaction described in step (1) are: by catalyzer G and Compound D
1Xbe dissolved in solvent F, obtain solvent system 1; Then compd E is dissolved in F, obtains solvent system 2; Be added drop-wise to by solvent system 2 in solvent system 1, rate of addition controls at 50 ~ 1000 μ L/min; After being added dropwise to complete, temperature of reaction system is elevated to 40 ~ 80 DEG C, continues reaction 1 ~ 5h, after reaction terminates, carry out precipitation with pentane and remove amine salt, the product obtained extracts lower boiling material by decompression, last product passed through silicagel column and carried out purifying, finally obtained colourless oil liquid D
1.
6. a solvent-free poly-organopolysiloxane mixture, is characterized in that: described solvent-free poly-organopolysiloxane mixture comprises spherical dendritic silicone macromolecule according to claim 1.
7. solvent-free poly-organopolysiloxane mixture according to claim 6, is characterized in that comprising as follows by the component of mass parts:
Spherical dendritic silicone macromolecule;
The content of described spherical dendritic silicone macromolecule is the spherical dendritic silicone macromolecule that every 100 mass parts alkenyls gather containing 0.1 ~ 10 weight part in the mixture of organopolysiloxane, polymethyl hydrogen siloxane, catalyzer and inhibitor.
8. solvent-free poly-organopolysiloxane mixture according to claim 7, is characterized in that:
The content of described spherical dendritic silicone macromolecule is the spherical dendritic silicone macromolecule that every 100 mass parts alkenyls gather containing 0.5 ~ 5 weight part in the mixture of organopolysiloxane, polymethyl hydrogen siloxane, catalyzer and inhibitor.
9. the preparation method of the solvent-free poly-organopolysiloxane mixture described in any one of claim 6 ~ 8, it is characterized in that comprising following steps: the component alkenyl of the solvent-free poly-organopolysiloxane mixture described in any one of claim 6 ~ 8 is gathered organopolysiloxane, polymethyl hydrogen siloxane, catalyzer, inhibitor and spherical dendritic silicone macromolecule and mixes, namely obtain solvent-free poly-organopolysiloxane mixture.
10. spherical dendritic silicone macromolecule according to claim 1 or the application of solvent-free poly-organopolysiloxane mixture in antiseized field described in any one of claim 6 ~ 8.
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| CN117567747A (en) * | 2024-01-16 | 2024-02-20 | 深圳先进电子材料国际创新研究院 | Surfactant for underfill, and preparation method and application thereof |
| CN117567747B (en) * | 2024-01-16 | 2024-04-09 | 深圳先进电子材料国际创新研究院 | Surfactant for underfill, and preparation method and application thereof |
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