CN106644813A - Analysis method of cross-linking degree of moisture-curable polyurethane - Google Patents
Analysis method of cross-linking degree of moisture-curable polyurethane Download PDFInfo
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Links
- 238000004132 cross linking Methods 0.000 title claims abstract description 65
- 238000004458 analytical method Methods 0.000 title claims abstract description 42
- 229920002635 polyurethane Polymers 0.000 title abstract description 11
- 239000004814 polyurethane Substances 0.000 title abstract description 11
- 238000012360 testing method Methods 0.000 claims abstract description 91
- 238000000605 extraction Methods 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000007789 sealing Methods 0.000 claims abstract description 5
- 238000013008 moisture curing Methods 0.000 claims description 49
- 150000003673 urethanes Chemical class 0.000 claims description 43
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229940113088 dimethylacetamide Drugs 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 238000005303 weighing Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 35
- 238000006116 polymerization reaction Methods 0.000 description 12
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- -1 polyoxyethylene propylene glycol Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101000598921 Homo sapiens Orexin Proteins 0.000 description 1
- 101001123245 Homo sapiens Protoporphyrinogen oxidase Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 102100029028 Protoporphyrinogen oxidase Human genes 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
Abstract
The invention relates to an analysis method of the cross-linking degree of moisture-curable polyurethane. The method comprises the following steps: feeding a moisture-curable polyurethane sample into a net-shaped covering object and sealing to obtain a testing sample; putting the obtained testing sample into an extraction device filled with a solvent; extracting the testing sample at a first temperature range of 60 DEG C to 90 DEG C, a second temperature range of 100 DEG C to 110 DEG C, a third temperature range of 120 DEG C to 130 DEG C and a fourth temperature range of 140 DEG C to 260 DEG C; after extracting, drying the testing sample and weighing; calculating the cross-linking degree of the testing sample according to an equation C=(m2-m0)/(m1-m0). According to the analysis method, the testing sample is extracted under the four different temperature ranges and is calculated, so that a cross-linking type and a ratio in the moisture-curable polyurethane are analyzed, and furthermore, performances of the moisture-curable polyurethane are analyzed; the analysis method has certain guidance meanings on formula, process and utilization condition selection of a moisture-curable polyurethane adhesive product.
Description
Technical field
The invention belongs to chemical field, is related to a kind of analysis method of the moisture cure urethanes degree of cross linking.
Background technology
In moisture cure urethanes adhesive contain active NCO group, when it is exposed in air, can with air in
Micro-moisture reacts；Hydroxyl, the amino isoreactivity hydrogen group that can also exist with the water of substrate surface absorption and surface
Generation chemical reaction, generates urea bond structure.Following five reactions will occur during its pre-polymerization and moisturecuring：
Wherein react Formulas I and II occurs mainly in precondensation stage, reaction Formula V occurs mainly in moisturecuring stage, reaction equation
III and IV is likely in pre-polymerization and moisturecuring stage to be occurred, wherein reaction Formulas I, III and IV have under certain condition substantially
Reaction invertibity.If above-mentioned respectively react the functional group that its component can participate in reacting containing two or more, crosslinking can be produced
Network structure；If containing two functional groups that can participate in reaction, only reacting III and IV can produce cross-linked structure.Further,
Pre-polymerization temperature, catalyst service condition, curing environment temperature and humidity etc. all can produce impact to above-mentioned reaction.
The A of CN 104280309 disclose a kind of method of testing of the photovoltaic module EVA encapsulating material degrees of cross linking, the photovoltaic
Component includes battery, is arranged at the backboard of cell backside and is arranged at the safety glass of battery front side, the battery and the steel
Change and be provided with EVA encapsulating material layers between glass, EVA encapsulating material layers are provided between the battery and the backboard, it is special
Levy and be, the method for testing is comprised the following steps：Photovoltaic module is chosen in step one, sampling, is sealed EVA using exfoliation tool
Package material layer is stripped out and to be cut into fragment stand-by, and selection weight is W1EVA encapsulating material layer fragments, by EVA encapsulating materials
It is W that layer fragment puts into weight2Stainless steel wire mesh bag in and seal and be made as sample bag, the weight for weighing sample bag is W3；Step
Two, boiling, the sample bag obtained in step one is put into digesting apparatus carries out boiling by reactant, and boiling to temperature is
110～120 DEG C and at this temperature keep 2～3min, then stop heating, be cooled to 30 DEG C；Step 3, circulates boiling, will
Sample bag is circulated boiling according to the order in step 2；Step 4, drying, by the examination after circulating boiling in step 3
Sample bag takes out, and hangs and removes volume drop, is then placed in being dried in vacuum drying box；Step 5, cooling, by step 4
Sample bag after drying is cooled down, and the weight that sample bag is weighed after cooling is W4；Step 6, calculates, using formula C=1-
(W3-W4)/(W3-W2) calculate EVA encapsulating materials the degree of cross linking.The method of testing, only tests EVA encapsulation under single temperature section
The degree of cross linking of material, and the cross-linking reaction in EVA encapsulating materials is not a kind of, the method can not accurately test various cross-linking reactions
Ratio, error is very big.
To sum up, the actual pre-polymerization of moisture cure urethanes adhesive and solidification process are extremely complex, and its cross-linked structure and crosslinking
Degree plays a decisive role to performance, but at this stage temporarily without a kind of effective method characterizing, so at present only by tentatively changing
Enter formula to reach some performance requirements.Therefore research one kind can accurately test the various cross-linking reaction crosslinkings of moisture cure urethanes
The method of degree and structure proportion is particularly significant.
The content of the invention
For problems of the prior art, the present invention provides a kind of analysis method of the moisture cure urethanes degree of cross linking,
The analysis method tests at different temperatures the degree of cross linking of different crosslinking methods, can be with the relatively accurate poly- ammonia of analysis moisturecuring
The cross-linked structure of ester, the formula, technique and use condition to moisture cure urethanes adhesive product is selected with certain guidance meaning
Justice.
It is that, up to this purpose, the present invention is employed the following technical solutions：
The present invention provides a kind of analysis method of the moisture cure urethanes degree of cross linking, the method comprising the steps of：
(1) moisture cure urethanes sample is fitted into netted coating, sealing obtains test sample；
(2) test sample that step (2) is obtained is put into the extraction device equipped with solvent, respectively in the first temperature section 60
140～260 DEG C of～90 DEG C, 100～110 DEG C of second temperature section, 120～130 DEG C of the 3rd temperature section and the 4th temperature section, to institute
State test sample to be stripped, extracting dries test sample after terminating, and weighs；
(3) according to formula C=(m2-m0)/(m1-m0) calculate test sample the degree of cross linking；
Wherein, in the formula C for test sample the degree of cross linking, m2For the matter of test sample after each temperature section extracting
Amount, m1For the quality of test sample before each temperature section extracting, m0For the quality of netted coating.
The temperature of first temperature section can be 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C；Described
The temperature of two temperature sections can be 100 DEG C, 101 DEG C, 102 DEG C, 103 DEG C, 104 DEG C, 105 DEG C, 106 DEG C, 107 DEG C, 108 DEG C, 109
DEG C or 110 DEG C etc.；The temperature of the 3rd temperature section can be 120 DEG C, 121 DEG C, 122 DEG C, 123 DEG C, 124 DEG C, 125 DEG C, 126 DEG C,
127 DEG C, 128 DEG C, 129 DEG C or 130 DEG C etc.；The temperature of the 4th temperature section can be 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180
DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 250 DEG C or 260 DEG C etc., it is not limited to cited number
Value, other included in above-mentioned each number range are that the numerical value enumerated is equally applicable.
When test sample is 1 group, test sample can be stripped at 60～90 DEG C, after extracting terminates, be taken out
Test sample, drying weighs the test sample weight after test；It is stripped at 100～110 DEG C, after extracting terminates, takes
Go out test sample, dry, weigh the test sample weight after test；On repeating at 120～130 DEG C and 140～260 DEG C
State test process.Finally calculate the degree of cross linking of sample under each temperature section.
It can be seen that when test sample is less than 4 groups, having least one set sample will carry out the survey of at least two temperature sections
Examination, and test sample is extracted under a temperature section and is finished during drying weighs and carry out another temperature section again, due to
The transfer of sample can cause the difficult quality of sample to avoid losing, and introduce error.On the other hand, even if in low temperature
The lower extracting of section, it is also difficult to which the decomposition reaction for having higher temperature section for avoiding occurs and causes error, sample is repeatedly taken out
Carrying can make this error be multiplied, while the test mode less than 4 groups will also result in the decline of testing efficiency, therefore the present invention
It is preferred that test sample is 4 groups.
When test sample be 4 groups when, four groups of test samples can be made at the same respectively 60～90 DEG C, 100～110 DEG C, 120
It is stripped under～130 DEG C and 140～260 DEG C of four temperature sections, extracting takes out test sample after terminating, dries, weighs and survey
Test sample weight after examination.Finally calculate total degree of cross linking of sample under each extraction temperature section.Calculate the single of each temperature section
The degree of cross linking need to deduct total degree of cross linking of a relatively low upper temperature section using total degree of cross linking of the temperature section, and temperature is minimum
The single degree of cross linking of first temperature section be its total degree of cross linking.
Every group of test sample at least contains three samples, and by repeatedly testing the method averaged the mistake of analysis is reduced
Difference.
As currently preferred technical scheme, step (1) the netted coating include irony mesh bag, copper mesh bag or
In aluminum mesh bag any one or at least two combination, combination typical case but non-limiting examples have：Irony mesh bag and copper
It is the combination of the combination of matter mesh bag, the combination of irony mesh bag and aluminum mesh bag, copper mesh bag and aluminum mesh bag or irony mesh bag, copper
Combination of mesh bag and aluminum mesh bag etc..
It is preferred that low, mesh number >=100 mesh of step (1) the netted coating, such as 100 mesh, 200 mesh, 250 mesh, 300 mesh,
350 mesh, 400 mesh, 500 mesh or 600 mesh etc., it is not limited to cited numerical value, other included in the number range are
The numerical value enumerated is equally applicable.
Used as currently preferred technical scheme, the temperature of step (2) first temperature section is 80～90 DEG C.
Preferably, the temperature of step (2) the second temperature section is 106～110 DEG C.
Preferably, the temperature of step (2) the 3rd temperature section is 120～125 DEG C.
Preferably, the temperature of step (2) the 4th temperature section is 200～210 DEG C.
Each cross-linked structure will not decompose at 60～90 DEG C of temperature range, i.e., what is now extracted is uncrosslinked portion
Point, test result is total degree of cross linking C of test sample0.It is preferred that 80～90 DEG C, dissolving of the solvent to test sample at a temperature of this is imitated
Rate is high, and higher than the fusing point of the components such as most polyalcohols and isocyanates.
100～110 DEG C of 106 DEG C of determinations of initial decomposition temperature according to reaction formula III back reaction of temperature range, reaction equation
Allophanate group on the right side of III can decompose reaction at 106 DEG C, regenerate carbamate groups and isocyanates
Base, as described above, the carbamate groups and NCO that produce after allophanate group cross-linked structure is decomposed are molten by solvent
Solution, then extraction tube is taken away by siphon, promote reaction to develop to the left, final allophanate group is decomposed completely, and test result is
Remove degree of cross linking C of allophanate group cross-linked network1.It is preferred that 106～110 DEG C, this temperature reaches rising for allophanate group
Beginning decomposition temperature, and less than the decomposition temperature of other cross-bonds.
Temperature range 120-130 DEG C reacts formula IV right according to 120 DEG C of determinations of initial decomposition temperature of reaction formula IV back reaction
The biuret groups of side can decompose reaction at 120 DEG C, regenerate urea groups and NCO, and test result is to remove urea
Degree of cross linking C of carbamate base and biuret groups cross-linked network2.It is preferred that 120～125 DEG C, this temperature reaches allophanate group
With the initial decomposition temperature of biuret groups, and less than the decomposition temperature of other cross-bonds.
Reaction Formulas I, R1And R2Respectively aryl and aryl, alkyl and aryl, aryl and alkyl, four kinds of feelings of alkyl and alkyl
Under condition, its back reaction, i.e. the initial decomposition temperature of right side carbamate groups is 120 DEG C, 180 DEG C, 200 DEG C, 250 DEG C, again
Generate NCO and hydroxyl.But in practical application, R2For aryl when, i.e. phenol is commonly used for the closure agent of blocked polyurethane,
Hardly it is used for moisture cure urethanes adhesive system, so R in moisture cure urethanes adhesive system2For alkyl, temperature model
Enclose 140-260 DEG C to determine therefrom that, test result is removing allophanate group, biuret groups and carbamate groups cross-linked network
Degree of cross linking C3, i.e. the degree of cross linking of urea groups cross-linked network.Generally, due to being rarely employed three aminated compounds as crosslinking
Agent, therefore urea groups cross-linked network is seldom present.It is preferred that 200～210 DEG C, 250～260 DEG C, due to R1For alkyl when, its isocyanates
Base activity is low, is only used for the occasion having high demands to aging xanthochromia, so more preferably 200～210 DEG C.
The degree of cross linking of moisture cure urethanes adhesive is C0, and allophanate group cross-linked network content is C0-C1, biuret
Base cross-linked network is C1-C2, carbamate groups cross-linked network content is C2-C3, urea groups cross-linked network content is C3。
To sum up, the present invention can not only test the degree of cross linking of moisture cure urethanes, simultaneously because different cross-linking reactions point
Solution temperature is different, by the degree of cross linking under analysis different temperatures section, can also analyze moisture cure urethanes internal crosslinking mechanism
Form and ratio.
Used as currently preferred technical scheme, step (2) extraction device includes extracting bottle, extraction tube and condensation
Device, the extracting bottle is connected with extraction tube by siphon pipe, and the condenser is connected with extracting bottle by connecting tube, the extracting
Top of bottle is joined directly together with condenser.
Wherein, extraction tube and extracting bottle are provided with the heater of controllable temperature, and the temperature of each temperature section is equal in step (2)
For the temperature in extraction tube；Preferably, connecting tube is likewise supplied with heating and heat preserving function, and its temperature setting is identical with extracting bottle, full
The process of Jing connecting tubes arrival extraction tube will not be condensed after sufficient solvent volatilization.
Used as currently preferred technical scheme, the siphon pipe is not less than the extracting with the junction of the extraction tube
The height of test sample in pipe.
Preferably, the siphon pipe and the junction of the extraction tube it is high higher than test sample in the extraction tube 2～4
Times, such as 2 times, 2.5 times, 3 times, 3.5 times or 4 times, it is not limited to cited numerical value, include in the number range its
He is that the numerical value enumerated is equally applicable.
As currently preferred technical scheme, during step (2) solvent is loaded on the extracting bottle, and the solvent
Liquid level is less than connecting tube and siphon pipe and the junction for extracting bottle.
Preferably, step (1) test sample is put in extraction tube.
When being stripped to test sample, heating extracting bottle makes solvent seethe with excitement, and steam is risen by connecting tube, is entered into cold
In condenser, instill after being condensed in extraction tube, solvent and test sample contact are stripped, when solvent liquid level reaches in extraction tube
During siphon threshold value, the solvent siphon for being dissolved with partial test sample returns to extracting bottle.Then extract bottle in solvent continue evaporate,
Condensation, backflow, siphon, so repeat, and test sample is constantly extracted by solvent, the crosslinking knot decomposed under this extraction temperature
Structure, such as reaction Formulas I, III and IV, because reaction equation left side component is constantly dissolved, and take away extraction tube, i.e. reaction equation with siphon
Left side constituent content is reduced, and promotes reaction to develop to the left, until right side component is decomposed completely.Hypothesis directly puts test sample
Put in a solvent, because reaction equation left and right sides component is present simultaneously, will equilibrium establishment, i.e. right side component as reversible reaction
Cannot decompose completely.
As currently preferred technical scheme, step (2) solvent include dimethylbenzene, DMF,
In dimethyl acetamide, dimethyl sulfoxide (DMSO) or 1-METHYLPYRROLIDONE any one or at least two combination, the combination allusion quotation
Type but non-limiting examples have：The combination of dimethylbenzene and N,N-dimethylformamide, N,N-dimethylformamide and dimethyl second
Combination or the diformazan of the combination of acid amides, the combination of dimethyl acetamide and dimethyl sulfoxide, dimethyl sulfoxide and 1-METHYLPYRROLIDONE
Combination of benzene, dimethyl sulfoxide (DMSO) and dimethyl acetamide etc..
The selection of above-mentioned solvent can have dissolubility to polyurethane, but do not react with polyurethane it is any known
Organic solvent, its boiling point necessarily be greater than the highest extraction temperature selected in test.
Used as currently preferred technical scheme, time of step (2) extracting is 7～12h, such as 7h, 8h, 9h,
10h, 11h or 12h etc., it is not limited to cited numerical value, other included in the number range are that the numerical value enumerated is same
Sample is suitable for, preferably 8～10h.
If extraction times decompose incomplete less than 7h samples, the test of the degree of cross linking can be caused inaccurate；If extraction times are big
In 12h, then efficiency reduces and wastes the energy.
Used as currently preferred technical scheme, step (2) drying is carried out in vacuum drying chamber.
As currently preferred technical scheme, temperature >=300 DEG C of the vacuum drying chamber, such as 300 DEG C, 400 DEG C,
500 DEG C, 600 DEG C, 700 DEG C or 800 DEG C etc., it is not limited to cited numerical value, other included in the number range are
The numerical value enumerated is equally applicable.
Preferably, the vacuum of the vacuum drying chamber is -0.1～-0.5MPa, such as -0.1MPa, -0.2MPa, -
0.3MPa, -0.4MPa or -0.5MPa etc., it is not limited to cited numerical value, other included in the number range are row
The numerical value of act is equally applicable.
Preferably, the time of step (2) drying is 2～4h, such as 2h, 2.5h, 3h, 3.5h or 4h, but and not only
It is limited to cited numerical value, other included in the number range are that the numerical value enumerated is equally applicable.
Compared with prior art, the present invention at least has the advantages that：
(1) the invention provides a kind of analysis method of the moisture cure urethanes degree of cross linking, the analysis method is using wet solid
Change polyurethane carries out chemical extracting in different decomposition temperature sections, quantitative fixed so as to obtain the degree of cross linking of different cross-linked structures
Cross-linked structure type and ratio in the analysis moisture cure urethanes sample of property.
(2) the invention provides a kind of analysis method of the moisture cure urethanes degree of cross linking, the analysis method is taken to taking out
Put forward the mode that bottle and extraction tube are respectively heated, it is ensured that solvent evaporate and selective dissolution effect, and by evaporation, it is cold
Solidifying, backflow, siphon make solvent Efficient Cycle, it is to avoid solute saturation and affect the problem that finally cannot decompose completely, with measurement
Error is little and simple to operate.
(3) the invention provides a kind of analysis method of the moisture cure urethanes degree of cross linking, the analysis method is to moisturecuring
The formula of adhesive for polyurethane product, technique and use condition select have certain guidance meaning.
Description of the drawings
Fig. 1 is the knot of the extraction device used in a kind of analysis method of moisture cure urethanes degree of cross linking that the present invention is provided
Structure schematic diagram；
In figure：1- extracts bottle, 2- extraction tubes, 3- condensers, 4- connecting tubes, 5- siphon pipes.
Specific embodiment
Specific embodiment of the invention part provides a kind of analysis method of the moisture cure urethanes degree of cross linking, and methods described includes
Following steps：
(1) moisture cure urethanes sample is fitted into netted coating, sealing obtains test sample；
(2) test sample that step (2) is obtained is put into the extraction device equipped with solvent, the extraction device such as Fig. 1
It is shown, respectively in 60～90 DEG C of the first temperature section, 100～110 DEG C of second temperature section, 120～130 DEG C of the 3rd temperature section and
Four 140～260 DEG C of temperature sections, are stripped to the test sample, and extracting dries test sample after terminating, and weighs；
(3) according to formula C=(m2-m0)/(m1-m0) calculate test sample the degree of cross linking；
Wherein, in the formula C for test sample the degree of cross linking, m2For the matter of test sample after each temperature section extracting
Amount, m1For the quality of test sample before each temperature section extracting, m0For the quality of netted coating.
For the present invention is better described, technical scheme is readily appreciated, the present invention's is typical but non-limiting
Embodiment is as follows：
The raw material of moisture cure urethanes is tested in specific embodiment of the invention part to be included：
ZSN-220：The molecular weight polyoxyethylene propylene glycol of 2 degree of functionality 2000, Jiangsu Zhongshang Chemical Co., Ltd.；
ZSN-330：The molecular weight polyoxyethylene propylene triol of 3 degree of functionality 3000, Jiangsu Zhongshang Chemical Co., Ltd.；
POL-356：The molecular weight polybutylene glyool adipate of 2 degree of functionality 2000, Qingdao Yu Tian Chemical Co., Ltd.s；
MDI-50：Methyl diphenylene diisocyanate, Wanhua Chemical Group Co., Ltd.；
Niax D-22：Dibutyl tin laurate, Momentive companies of the U.S.；
HF-3H95：PAUR elastomer, Zhejiang Province Huafeng New materials Co., Ltd.
Embodiment 1
A kind of analysis method of the moisture cure urethanes degree of cross linking, the method comprising the steps of：
(1) moisture cure urethanes sample is fitted into irony mesh bag, sealing obtains test sample；
(2) test sample that step (2) is obtained is put into the extraction device equipped with NMP, respectively in the first temperature section 85
DEG C, 110 DEG C of second temperature section, 120 DEG C of the 3rd temperature section and 200 DEG C of the 4th temperature section, the test sample is stripped
8h, extracting dries test sample after terminating, and weighs；
(3) according to formula C=(m2-m0)/(m1-m0) calculate test sample the degree of cross linking；
Wherein, in the formula C for test sample the degree of cross linking, m2For the matter of test sample after each temperature section extracting
Amount, m1 is the quality of test sample before the extracting of each temperature section, m0For the quality of netted coating.
The moisture cure urethanes that the present embodiment is adopted is 28g ZSN-220,7.38g ZSN-330 and 68g MDI-50,
The pre-polymerization 120min at 80 DEG C, prepares after solidifying 7 days under 25 DEG C and 50%RH.
Embodiment 2
A kind of analysis method of the moisture cure urethanes degree of cross linking, after methods described is except the raw material pre-polymerization of moisture cure urethanes
Beyond the highest heavens, other conditions are same as Example 1 for solidification 7 under 15 DEG C and 30%RH.
Embodiment 3
A kind of analysis method of the moisture cure urethanes degree of cross linking, except the raw material pre-polymerization temperature of moisture cure urethanes is 100
Outside DEG C, other conditions are same as Example 1.
Embodiment 4
A kind of analysis method of the moisture cure urethanes degree of cross linking, except moisture cure urethanes raw material be 12g ZSN-220,
Outside 24g POL-356,5.38g ZSN-330 and 74g MDI-50, other conditions are same as Example 1.
Embodiment 5
A kind of analysis method of the moisture cure urethanes degree of cross linking, except the raw material of moisture cure urethanes is 33g ZSN-220
And outside 62gMDI-50, other conditions are same as Example 1.
Embodiment 6
A kind of analysis method of the moisture cure urethanes degree of cross linking, except moisture cure urethanes raw material be 31g ZSN-220,
Outside 0.8g water and 61.2gMDI-50, other conditions are same as Example 1.
Embodiment 7
A kind of analysis method of the moisture cure urethanes degree of cross linking, except moisture cure urethanes raw material be 33g ZSN-220,
62gMDI-50 and 0.16g Niax D-22, pre-polymerization temperature be 120 DEG C, the pre-polymerization time be 60min outside, other conditions with reality
Apply example 1 identical.
Embodiment 8
A kind of analysis method of the moisture cure urethanes degree of cross linking, except 60 DEG C of the first temperature section, second temperature in step (2)
140 DEG C of 100 DEG C of section, 120 DEG C of the 3rd temperature section and the 4th temperature section, solvent selects dimethyl sulfoxide (DMSO), and extraction times are 12h
Outward, other conditions are same as Example 1.
Embodiment 9
A kind of analysis method of the moisture cure urethanes degree of cross linking, except 90 DEG C of the first temperature section, second temperature in step (2)
260 DEG C of 110 DEG C of section, 130 DEG C of the 3rd temperature section and the 4th temperature section, solvent selects dimethyl acetamide, and extraction times are 7h
Outward, other conditions are same as Example 1.
Embodiment 10
A kind of analysis method of the moisture cure urethanes degree of cross linking, except 80 DEG C of the first temperature section, second temperature in step (2)
210 DEG C of 106 DEG C of section, 125 DEG C of the 3rd temperature section and the 4th temperature section, solvent selects DMF, extraction times
Outside for 10h, other conditions are same as Example 1.
Comparative example 1
A kind of analysis method of the moisture cure urethanes degree of cross linking, in addition to test sample adopts HF-3H95, other conditions are equal
It is same as Example 1.
As shown in table 1, test result is as shown in table 2 for the composition of raw materials of above-described embodiment 1-10 and comparative example 1.
Table 1
Table 2
| Pre-polymerization condition | Condition of cure | C0 | C1 | C2 | C3 | X | Y | Z | |
| Embodiment 1 | 80℃/120min | 25 DEG C/50%RH | 100% | 85% | 82% | 0% | 15% | 3% | 82% |
| Embodiment 2 | 80℃/120min | 15 DEG C/30%RH | 90% | 77% | 77% | 0% | 13% | 0% | 77% |
| Embodiment 3 | 100℃/120min | 25 DEG C/50%RH | 100% | 81% | 81% | 0% | 19% | 0% | 81% |
| Embodiment 4 | 80℃/120min | 25 DEG C/50%RH | 100% | 79% | 72% | 0% | 21% | 7% | 72% |
| Embodiment 5 | 80℃/120min | 25 DEG C/50%RH | 82% | 12% | 0% | 0% | 70% | 12% | 0% |
| Embodiment 6 | 80℃/120min | 25 DEG C/50%RH | 83% | 32% | 0% | 0% | 51% | 32% | 0% |
| Embodiment 7 | 120℃/60min | 25 DEG C/50%RH | 90% | 2% | 0% | 0% | 88% | 2% | 0% |
| Embodiment 8 | 80℃/120min | 25 DEG C/50%RH | 100% | 83% | 80% | 0% | 17% | 3% | 80% |
| Embodiment 9 | 80℃/120min | 25 DEG C/50%RH | 100% | 86% | 83% | 0% | 14% | 3% | 83% |
| Embodiment 10 | 80℃/120min | 25 DEG C/50%RH | 100% | 85% | 82% | 0% | 15% | 3% | 82% |
| Comparative example 1 | 0% | 0% | 0% | 0% | 0% | 0% | 0% |
In table 2, X：The content of allophanate group cross-linked network, Y：The content of biuret groups cross-linked network, Z：Amino first
The content of perester radical cross-linked network.
Comparative example 1 and 2, and temperature and humidity is reduced in theory, unfavorable to moisturecuring process, i.e., to reacting formula III, IV
Unfavorable with the reaction shown in V, the degree of cross linking is reduced, consistent with test result trend.
Comparative example 1 and 3, and pre-polymerization temperature is improved in theory, and the reaction that increased carbamate and isocyanates is lived
Property, that is, reacting the content of reaction shown in formula III, i.e. allophanate group cross-linked network increases, consistent with test result trend.
Comparative example 1,4 and 5, and in theory three-functionality-degree PPOX triol usage amount is reduced, and can make carbamic acid
The content of ester group cross-linked network is reduced, consistent with test result trend.
Comparative example 5 and 7, use catalyst in pre- collecting process in theory, on the one hand can accelerate NCO and hydroxyl
The reaction of base, that is, react the reaction shown in Formulas I；On the other hand the reaction of carbamate groups and NCO can also be accelerated,
I.e. react formula III shown in reaction, its effect with raising pre-polymerization temperature effect as, the content of allophanate group cross-linked network
Increase, it is consistent with test result trend.
Comparative example 1,8,9 and 10, change within the temperature range of regulation in the temperature section of step (2) first, second warm
The temperature of the temperature section of degree section the 3rd temperature section the 4th, while during solvent and extracting in replacement step (2) in prescribed limit
Between, the test result and embodiment 1 of embodiment 8,9 and 10 is basically identical, and error is within zone of reasonableness.
Comparative example 3H-95 is PAUR elastomer, and in theory it does not have cross-linked structure, with test result trend
Unanimously.
Applicant states that the present invention illustrates the detailed construction feature of the present invention by above-described embodiment, but the present invention is simultaneously
Above-mentioned detailed construction feature is not limited to, that is, does not mean that the present invention has to rely on above-mentioned detailed construction feature and could implement.Institute
Category those skilled in the art are it will be clearly understood that any improvement in the present invention, the equivalence replacement to part selected by the present invention
And increase, the selection of concrete mode of accessory etc., within the scope of all falling within protection scope of the present invention and disclosure.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, the present invention range of the technology design in, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as it is without prejudice to this
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of analysis method of the moisture cure urethanes degree of cross linking, it is characterised in that the method comprising the steps of：
(1) moisture cure urethanes sample is fitted into netted coating, sealing obtains test sample；
(2) test sample that step (2) is obtained is put into the extraction device equipped with solvent, respectively in the first temperature section 60～90
DEG C, 100～110 DEG C of second temperature section, 120～130 DEG C of the 3rd temperature section and 140～260 DEG C of the 4th temperature section, to the survey
Test agent is stripped, and extracting dries test sample after terminating, and weighs；
(3) according to formula C=(m2-m0)/(m1-m0) calculate the degree of cross linking of the test sample in each temperature section；
Wherein, in the formula C for test sample the degree of cross linking, m2For the quality of test sample after each temperature section extracting, m1
For the quality of test sample before each temperature section extracting, m0For the quality of netted coating.
2. analysis method according to claim 1, it is characterised in that step (1) the netted coating includes irony net
In bag, copper mesh bag or aluminum mesh bag any one or at least two combination；
It is preferred that low, mesh number >=100 mesh of step (1) the netted coating.
3. analysis method according to claim 1 and 2, it is characterised in that the temperature of step (2) first temperature section is
80～90 DEG C；
Preferably, the temperature of step (2) the second temperature section is 106～110 DEG C；
Preferably, the temperature of step (2) the 3rd temperature section is 120～125 DEG C；
Preferably, the temperature of step (2) the 4th temperature section is 200～210 DEG C.
4. the analysis method according to any one of claim 1-3, it is characterised in that step (2) extraction device includes
Extracting bottle, extraction tube and condenser, the extracting bottle is connected with extraction tube by siphon pipe, and the condenser and extracting bottle pass through
Connecting tube is connected, and the extracting top of bottle is joined directly together with condenser.
5. analysis method according to claim 4, it is characterised in that step (2) siphon pipe and the extraction tube
Junction is not less than the height of test sample in the extraction tube；
Preferably, 2～4 times high higher than test sample in the extraction tube in the siphon pipe and the junction of the extraction tube.
6. the analysis method according to any one of claim 3-5, it is characterised in that step (2) solvent is loaded on described
In extracting bottle, and the liquid level of the solvent is less than connecting tube and siphon pipe and the junction for extracting bottle；
Preferably, step (1) test sample is put in extraction tube.
7. the analysis method according to any one of claim 1-6, it is characterised in that step (2) solvent includes diformazan
In benzene, N,N-dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO) or 1-METHYLPYRROLIDONE any one or at least two
The combination planted.
8. the analysis method according to any one of claim 1-7, it is characterised in that the time of step (2) extracting is 7
～12h, preferably 8～10h.
9. the analysis method according to any one of claim 1-8, it is characterised in that step (2) drying is dry in vacuum
Carry out in dry case.
10. analysis method according to claim 9, it is characterised in that temperature >=300 DEG C of the vacuum drying chamber；
Preferably, the vacuum of the vacuum drying chamber is -0.1～-0.5MPa；
Preferably, the time of step (2) drying is 2～4h.
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