CN113307926A - Polyurethane acrylate with higher elongation at break and preparation method thereof - Google Patents
Polyurethane acrylate with higher elongation at break and preparation method thereof Download PDFInfo
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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- C08G18/67—Unsaturated compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G2170/00—Compositions for adhesives
Abstract
The invention belongs to the technical field of functional polymer materials, and particularly relates to polyurethane acrylate with high elongation at break and a preparation method thereof. The invention obtains the resin composition with the stretching rate of more than 600 percent by using polycaprolactone diol as a soft segment, IPDI and a chain extender as a hard segment and IBOA as a diluent and terminating with HEMA after synthesizing a prepolymer.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to polyurethane acrylate with high elongation at break and a preparation method thereof.
Background
The ultraviolet curing technology has the advantages of environmental friendliness, rapid curing, less energy consumption, high production efficiency, good coating performance and the like, and is rapidly developed in the fields of chemical industry, electronic industry, transportation and the like. The photocuring technology mainly comprises coatings, printing ink, adhesives, some wood lacquer and the like, the main body of the photocuring technology is composed of UV resin, UV monomers, photoinitiators, auxiliaries and the like, and the film forming material performance is mainly provided by the resin as is well known. Conventional resins are mainly epoxy acrylates, urethane acrylates, polyester acrylates, polyether acrylates and the like.
In particular applications, such as leather, adhesives and 3C coatings, the film formers are required to have extremely high elongation and bending resistance, which places extremely high demands on the resins. In the conventional UV resin, the common stretching ratio of epoxy acrylate, polyester acrylate, polyether acrylate and the like does not exceed 100%, and the polyurethane acrylate has the performances of good stretching, good wear resistance and the like in the aspect of mechanical properties compared with the above types of resins, but for special requirements of high stretching, high bending and the like, the conventional commercially available products are difficult to meet the use requirements. The prior patent literature discloses that 2-6 functional polyurethane acrylate is prepared by using diisocyanate as a hard segment, polycaprolactone diol as a soft segment, side chain-containing diol as a chain extender, PETA, HEA and the like as end capping agents, and the breaking elongation of the polyurethane acrylate is between 200 and 300 percent. Still other patent documents disclose that the elongation of urethane acrylate prepared by using polytetrahydrofuran diol as soft segment, IPDI as hard segment, ethylene glycol as chain extender, and ethoxyethoxyethyl acrylate as diluent is between 200 and 300%, and the urethane acrylate can achieve better stretching and bending resistance for conventional stretching requirements, but is difficult to achieve for the elongation of hundreds of folds and film-forming materials being more than 200%. The elongation at break of the polyurethane acrylate composition in the prior art cannot meet the requirement, and the elongation at break of the polyurethane acrylate composition needs to be further improved.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to overcome the defect that the elongation at break of the urethane acrylate in the prior art still needs to be further improved, thereby providing a urethane acrylate with a higher elongation at break and a preparation method thereof.
Therefore, the invention provides the following technical scheme:
the invention provides a preparation method of polyurethane acrylate with higher elongation at break, which comprises the following steps:
prepolymer preparation: synthesizing a prepolymer by using polycaprolactone diol as a soft segment, isophorone diisocyanate and a chain extender as a hard segment and isobornyl acrylate as a diluent;
preparation of urethane acrylate: and (3) terminating the obtained prepolymer by adopting hydroxyethyl methacrylate to obtain the polyurethane acrylate.
Optionally, the reaction temperature of the prepolymer synthesis step is 70-80 ℃, and the reaction time is 1-3 h.
Optionally, the preparation method of the urethane acrylate with high elongation at break comprises the following specific steps:
uniformly mixing polycaprolactone diol, isophorone diisocyanate, a chain extender, isobornyl acrylate, a catalyst and a polymerization inhibitor, and reacting to obtain a prepolymer;
and adding an end-capping reagent hydroxyethyl methacrylate after the NCO is lower than the theoretical NCO to obtain the polyurethane acrylate.
Optionally, the molar ratio of the materials isophorone diisocyanate: polycaprolactone diol: the chain extender is 2: (0.95-1): (0.7-0.75), IOBA accounts for (28-32)% of the total material.
Optionally, the molecular weight of the polycaprolactone diol is 950-1050, and 1, 6-hexanediol is used as an initiator;
the chain extender is one of diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol and hydrogenated bisphenol A; preferably, the chain extender is diethylene glycol.
Optionally, the catalyst is any one of dibutyltin dilaurate, dibutyltin laurate, an organic silver catalyst, an organic bismuth catalyst and an organic bismuth/organic zinc mixed catalyst;
the polymerization inhibitor is any one of p-hydroxyanisole and 2, 6-di-tert-butyl-p-cresol.
Optionally, the dosage of the catalyst is 0.05-0.1% of the total mass of the reaction system materials;
the dosage of the polymerization inhibitor is 0.05-0.1% of the total mass of the materials of the reaction system.
The invention provides urethane acrylate with higher elongation at break, which is prepared by the preparation method.
Alternatively, the molecular weight of the urethane acrylate having a higher elongation at break is 20000-30000.
Optionally, the urethane acrylate having a higher elongation at break has a glass transition temperature of-20 ℃ to 10 ℃; the elongation at break is more than or equal to 600 percent.
The invention takes polycaprolactone with excellent flexibility as a main chain, IPDI as an isocyanate hard segment, IBOA as a diluent, chain extension is carried out twice by using a chain extender, and finally end capping is carried out by using HEMA to obtain the resin composition with the stretching rate more than 600%.
The technical scheme of the invention has the following advantages:
the preparation method of the polyurethane acrylate with higher elongation at break provided by the invention comprises the following steps: prepolymer preparation: synthesizing a prepolymer by using polycaprolactone diol as a soft segment, isophorone diisocyanate and a chain extender as a hard segment and isobornyl acrylate as a diluent; preparation of urethane acrylate: and (3) terminating the obtained prepolymer by adopting hydroxyethyl methacrylate to obtain the polyurethane acrylate. According to the method, the polyurethane acrylate with the elongation at break of more than 600% can be prepared by matching the raw material components, and the use requirements in the fields of automotive interior trim, peelable blue glue, adhesives and the like are met. In addition, the method is simple to operate, and the target product can be obtained only through conventional chain extension and end capping reactions.
According to the preparation method of the urethane acrylate with high elongation at break, the reaction temperature of the prepolymer synthesis step is 70-80 ℃, and the reaction time is 1-3 h. So limited, the chain extension reaction can be fully carried out, and the phenomenon of uneven stirring caused by too large viscosity during the reaction of reactants can be ensured.
The preparation method of the polyurethane acrylate with higher elongation at break provided by the invention comprises the following specific steps: uniformly mixing polycaprolactone diol, isophorone diisocyanate, a chain extender, isobornyl acrylate, a catalyst and a polymerization inhibitor, and reacting to obtain a prepolymer; and adding an end-capping reagent hydroxyethyl methacrylate after the NCO is lower than the theoretical NCO to obtain the polyurethane acrylate. The method has simple steps and is convenient for industrial popularization.
The molecular weight of the urethane acrylate with higher elongation at break provided by the invention is 20000-30000, so that the main chain of the polymerized resin is longer, and the resin film-forming material with extremely high elongation is obtained.
The glass transition temperature of the polyurethane acrylate with high elongation at break is-20 ℃ to 10 ℃, so that the resin film-forming material can be ensured to rotate and stretch molecular main chains at daily use temperature, and the resin film-forming material has extremely high stretch rate when the stretch rate is tested.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
This example provides a method for preparing urethane acrylate with high elongation at break, comprising the following steps,
prepolymer preparation:
adding 40.01kg of IPDI, 90kg of PCl1000 (polycaprolactone diol with the molecular weight of 1000 (1, 6-hexanediol is used as an initiator), 0.213kg of p-hydroxyanisole, 7.16kg of DEG, 63.81kg of IBOA and 0.106kg of dibutyltin laurate into a reaction kettle, introducing dry air, heating to 70 ℃, keeping constant, and reacting until NCO is lower than 0.94% to obtain a prepolymer;
preparation of urethane acrylate:
adding 11.71kg of HEMA into the reaction kettle, heating to 75 ℃, keeping the temperature, measuring NCO after 2h, stopping the reaction when the NCO residue is less than 0.05%, filtering and discharging.
Example 2
This example provides a method for preparing urethane acrylate with high elongation at break, comprising the following steps,
adding 35.57kg of IPDI, 80kg of PCl1000 (polycaprolactone diol, 1000 molecular weight (1, 6-hexanediol is used as an initiator), 0.188kg of p-hydroxyanisole, 5.407kg of 1, 4-butanediol, 56.43kg of IBOA and 0.094kg of dibutyltin laurate into a reaction kettle, introducing dry air, heating to 70 ℃, keeping constant, and reacting until NCO is lower than 0.94% to obtain a prepolymer;
preparation of urethane acrylate:
and adding 10.41kg of HEMA into the reaction kettle, heating to 75 ℃, keeping the temperature, measuring NCO after 2 hours, stopping the reaction when the NCO residue is less than 0.05 percent, filtering and discharging.
Example 3
This example provides a method for preparing urethane acrylate with high elongation at break, comprising the following steps,
prepolymer preparation:
putting 44.458kg of IPDI, 100kg of PCl1000 (polycaprolactone diol, 1000 molecular weight (1, 6-hexanediol is used as an initiator), 0.238kg of p-hydroxyanisole, 7.75kg of DEG, 71.41kg of IBOA and 0.119kg of dibutyltin laurate in a reaction kettle, introducing dry air, heating to 70 ℃, keeping constant, and reacting until NCO is lower than 1.02% to obtain a prepolymer;
preparation of urethane acrylate:
and (3) adding 14.06kg of HEMA into the reaction kettle, heating to 75 ℃, keeping the temperature, measuring NCO after 2 hours, stopping the reaction when the NCO residue is less than 0.05%, filtering and discharging.
Example 4
This example provides a method for preparing urethane acrylate with high elongation at break, comprising the following steps,
prepolymer preparation:
putting 42.12kg of IPDI, 90kg of PCl1000 (polycaprolactone diol with the molecular weight of 1000 (1, 6-hexanediol is used as an initiator), 0.109kg of p-hydroxyanisole, 7.92kg of DEG, 65.70kg of IBOA and 0.109kg of dibutyltin laurate in a reaction kettle, introducing dry air, heating to 70 ℃, keeping constant, and reacting until NCO is lower than 1.01% to obtain a prepolymer;
preparation of urethane acrylate:
and (3) adding 12.95kg of HEMA into the reaction kettle, heating to 75 ℃, keeping the temperature, measuring NCO after 2 hours, stopping the reaction when the NCO residue is less than 0.05%, filtering and discharging.
Example 5
This example provides a method for preparing urethane acrylate with high elongation at break, comprising the following steps,
prepolymer preparation:
adding 40.01kg of IPDI, 90kg of PCl1000 (polycaprolactone diol, 1000 molecular weight (1, 6-hexanediol is used as an initiator), 0.106kg of 2, 6-di-tert-butyl-4-methylphenol, 7.16kg of DEG, 634.81kg of IBOA and 0.106kg of dibutyltin laurate into a reaction kettle, introducing dry air, heating to 70 ℃, keeping constant, and reacting until NCO is lower than 0.93% to obtain a prepolymer;
preparation of urethane acrylate:
adding 11.71kg of HEMA into the reaction kettle, heating to 75 ℃, keeping the temperature, measuring NCO after 2h, stopping the reaction when the NCO residue is less than 0.05%, filtering and discharging.
Example 6
This example provides a method for preparing urethane acrylate with high elongation at break, comprising the following steps,
prepolymer preparation:
putting 48.90kg of IPDI, 110kg of PCl1000 (polycaprolactone diol, 1000 molecular weight (1, 6-hexanediol is used as an initiator), 0.264kg of p-hydroxyanisole, 8.75kg of DEG, 81.93kg of IBOA and 0.127kg of dibutyltin laurate in a reaction kettle, introducing dry air, heating to 70 ℃, keeping constant, and reacting until NCO is lower than 0.92% to obtain a prepolymer;
preparation of urethane acrylate:
and (3) adding 14.32kg of HEMA into the reaction kettle, heating to 80 ℃, keeping the temperature, measuring NCO after 2 hours, stopping the reaction when the NCO residue is less than 0.05%, filtering and discharging.
Example 7
This example provides a method for preparing urethane acrylate with high elongation at break, comprising the following steps,
prepolymer preparation:
adding 40.01kg of IPDI, 90kg of PCl1000 (polycaprolactone diol with the molecular weight of 1000 (1, 6-hexanediol is used as an initiator), 0.213kg of p-hydroxyanisole, 7.16kg of DEG, 63.81kg of IBOA and 0.106kg of dibutyltin laurate into a reaction kettle, introducing dry air, heating to 70 ℃, keeping constant, and reacting until NCO is lower than 0.94% to obtain a prepolymer;
preparation of urethane acrylate:
adding 11.71kg of HEMA into the reaction kettle, heating to 70 ℃, keeping the temperature, measuring NCO after 2 hours, stopping the reaction when the NCO residue is less than 0.05 percent, filtering and discharging.
Comparative example 1
This comparative example provides a method for preparing urethane acrylate having a higher elongation at break, comprising the steps of,
prepolymer preparation:
adding 40.01kg of IPDI (isophorone diisocyanate), 90kg of PCl1000 (polycaprolactone diol, 1000 molecular weight, 1, 6-hexanediol as an initiator), 0.211kg of p-hydroxyanisole, 7.16kg of DEG, 63.40kg of IBOA (isopropyl-beta-hydroxy-phenyl) and 0.106kg of dibutyltin laurate into a reaction kettle, introducing dry air, heating to 70 ℃, keeping constant, and reacting until NCO is lower than 0.94% to obtain a prepolymer;
preparation of urethane acrylate:
and adding 10.45kg of HEA into the reaction kettle, heating to 75 ℃, keeping the temperature, measuring NCO after 2 hours, stopping the reaction when the NCO residue is less than 0.05%, filtering and discharging.
Comparative example 2
This comparative example provides a method for preparing urethane acrylate having a higher elongation at break, comprising the steps of,
prepolymer preparation:
adding 80.02kg of IPDI, 90kg of PCl1000 (polycaprolactone diol with the molecular weight of 1000 (1, 6-hexanediol is used as an initiator), 0.324kg of p-hydroxyanisole, 21.49kg of DEG, 97.34kg of IBOA and 0.162kg of dibutyltin laurate into a reaction kettle, introducing dry air, heating to 70 ℃, keeping constant, and reacting until NCO is lower than 1.97% to obtain a prepolymer;
preparation of urethane acrylate:
35.14kg of HEMA is added into the reaction kettle, the temperature is raised to 75 ℃, the temperature is kept, NCO is measured after 2 hours, the reaction is stopped when the NCO residue is lower than 0.05 percent, and the materials are filtered and discharged.
Comparative example 3
This comparative example provides a method for preparing urethane acrylate having a higher elongation at break, comprising the steps of,
prepolymer preparation:
putting 40.01kg of IPDI (isophorone diisocyanate), 90kg of PCl1000 (polycaprolactone diol, 1000 molecular weight, 1, 6-hexanediol as an initiator), 0.213kg of p-hydroxyanisole, 7.16kg of DEG, 63.81kg of TPGDA (tripropylene glycol diacrylate) and 0.106kg of dibutyltin laurate into a reaction kettle, introducing dry air, heating to 70 ℃, keeping constant, and reacting until NCO is lower than 0.94% to obtain a prepolymer;
preparation of urethane acrylate:
adding 11.71kg of HEMA into the reaction kettle, heating to 75 ℃, keeping the temperature, measuring NCO after 2h, stopping the reaction when the NCO residue is less than 0.05%, filtering and discharging.
Test examples
1. Elongation at break test
100g of the urethane acrylate resins prepared in examples 1 to 7 and comparative examples 1 to 3 were added with 3g of 184 g of initiator (1-hydroxycyclohexyl phenyl ketone), and the mixture was uniformly stirred and dissolved, and then the mixture was drawn on release paper to form a film with a thickness of 0.2 mm. After curing by a UV machine, 5 groups of sample strips were cut from the obtained urethane acrylate resin cured films by a dumbbell cutter according to national standard GB1040-79, and the elongation at break was measured on an Instron 2366 type electronic universal tester and averaged. The test results are shown in the following table:
2. glass transition temperature test
Preparation of sample strips: respectively taking 100g of the polyurethane acrylate resin prepared in the examples 1-7 and the comparative examples 1-3, respectively adding 3g of 184 initiator (1-hydroxycyclohexyl benzophenone), uniformly stirring, dissolving, then blade-coating on release paper to form a film with the thickness of 0.2mm, and carrying out a sample retention test;
test methods reference is made to the american society for testing and materials, standard for the method glass transition DMA transition temperature, ASTM D7028-2007 (2015).
3. Molecular weight measurement
Equipment/reagents: GPC (Waters e2695+ detector 2414), electronic balance, chromatographic grade tetrahydrofuran (mobile phase), chromatographic grade isopropanol (lubricating plunger rod).
Sample preparation:
0.125g of the urethane acrylate resin prepared in examples 1 to 7 and comparative examples 1 to 3 was weighed, 6mL of tetrahydrofuran was added, the mixture was left to stand for half an hour to be completely dissolved, the dissolved sample was filtered by a disposable filter (generally 0.45 um) and then transferred to a sample bottle, and the volume of the sample in the sample bottle was larger than 1/3 of the sample bottle. Detectable after 1 hour of standing.
And (3) testing: testing according to the method specified by GPC instrument.
TABLE 1
As can be seen from the data in the table, the present invention can prepare a high tensile resin composition with an elongation at break of > 600%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A preparation method of urethane acrylate with higher elongation at break is characterized by comprising the following steps:
prepolymer preparation: synthesizing a prepolymer by using polycaprolactone diol as a soft segment, isophorone diisocyanate and a chain extender as a hard segment and isobornyl acrylate as a diluent;
preparation of urethane acrylate: and (3) terminating the obtained prepolymer by adopting hydroxyethyl methacrylate to obtain the polyurethane acrylate.
2. The method for preparing urethane acrylate having high elongation at break according to claim 1, wherein the reaction temperature of the step of synthesizing the prepolymer is 70-80 ℃ and the reaction time is 1-3 hours.
3. The method for preparing urethane acrylate with higher elongation at break according to claim 2, characterized by comprising the following steps:
uniformly mixing polycaprolactone diol, isophorone diisocyanate, a chain extender, isobornyl acrylate, a catalyst and a polymerization inhibitor, and reacting to obtain a prepolymer;
and adding an end-capping reagent hydroxyethyl methacrylate after the NCO is lower than the theoretical NCO to obtain the polyurethane acrylate.
4. The method for preparing urethane acrylate with higher elongation at break according to claims 1 to 3, wherein the molar ratio of the materials isophorone diisocyanate: polycaprolactone diol: the chain extender is 2: (0.95-1): (0.7-0.75), IOBA accounts for (28-32)% of the total material.
5. The method for preparing urethane acrylate with higher elongation at break according to any of claims 1-3, wherein the molecular weight of polycaprolactone diol is 950-1050, 1, 6-hexanediol is used as initiator;
the chain extender is a difunctional chain extender, and optionally, the chain extender is one of diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol and hydrogenated bisphenol A; preferably, the chain extender is diethylene glycol.
6. The method for preparing urethane acrylate with higher elongation at break according to claim 3, wherein the catalyst is any one of dibutyltin dilaurate, dibutyltin laurate, an organic silver catalyst, an organic bismuth/organic zinc mixed catalyst;
the polymerization inhibitor is any one of p-hydroxyanisole and 2, 6-di-tert-butyl-p-cresol.
7. The method for preparing urethane acrylate with higher elongation at break according to claim 6, wherein the amount of the catalyst is 0.05-0.1% of the total mass of the reaction system materials;
the dosage of the polymerization inhibitor is 0.05-0.1% of the total mass of the materials of the reaction system.
8. A urethane acrylate having a high elongation at break, which is produced by the production method according to any one of claims 1 to 6.
9. The urethane acrylate with higher elongation at break according to claim 8, wherein the molecular weight of the urethane acrylate with higher elongation at break is 20000-30000.
10. The urethane acrylate with higher elongation at break according to claim 8 or 9, wherein the urethane acrylate with higher elongation at break has a glass transition temperature of-20 ℃ to 10 ℃; the elongation at break is more than or equal to 600 percent.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700024A (en) * | 2015-11-15 | 2017-05-24 | 惠州市长润发涂料有限公司 | Preparation method of UV-curable polyurethane acrylate self-repair resin |
| CN108727550A (en) * | 2018-04-23 | 2018-11-02 | 浙江锐胜新材料有限公司 | A kind of photosensitive resin and its application |
| CN112029060A (en) * | 2020-08-11 | 2020-12-04 | 大赛璐（中国）投资有限公司 | Photo-curing polyurethane acrylate resin composition and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700024A (en) * | 2015-11-15 | 2017-05-24 | 惠州市长润发涂料有限公司 | Preparation method of UV-curable polyurethane acrylate self-repair resin |
| CN108727550A (en) * | 2018-04-23 | 2018-11-02 | 浙江锐胜新材料有限公司 | A kind of photosensitive resin and its application |
| CN112029060A (en) * | 2020-08-11 | 2020-12-04 | 大赛璐（中国）投资有限公司 | Photo-curing polyurethane acrylate resin composition and preparation method and application thereof |
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Application publication date: 20210827 |