CN115975150A - Organic silicon modified thermoplastic polyurethane resin for 3D printing and preparation method thereof - Google Patents
Organic silicon modified thermoplastic polyurethane resin for 3D printing and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of 3D printing thermoplastic polyurethane materials, and particularly relates to organic silicon modified thermoplastic polyurethane resin for 3D printing and a preparation method thereof. The organic silicon modified thermoplastic polyurethane resin for 3D printing comprises a component A and a component B, wherein the component A is an-OH end-capped polyurethane prepolymer prepared by the reaction of polyol and isocyanate, and the R value is 0.95 to 0.98; the component B comprises-NCO end-blocked organosilane and a catalyst; the molar ratio of-OH in the component A to-NCO in the component B is 1. The invention improves the temperature resistance of polyurethane resin and the mechanical strength of the melt, thereby ensuring the feeding stability when the polyurethane resin is used for 3D printing, and having good mechanical property and better melt fluidity. The invention also provides a scientific and reasonable preparation method.
Description
Technical Field
The invention belongs to the technical field of 3D printing thermoplastic polyurethane materials, and particularly relates to organic silicon modified thermoplastic polyurethane resin for 3D printing and a preparation method thereof.
Background
The 3D printing technology is a rapid prototyping technology, also called additive manufacturing technology, which is a technology for constructing an object by using a bondable material such as plastic or metal in the form of strips, flakes or powder particles by printing layer by layer on the basis of a digital model file. Thermoplastic Polyurethane (TPU) is also widely used for 3D printing and forming of various parts due to excellent material properties, and the current 3D printing and forming technology of TPU materials mainly includes Fused Deposition Modeling (FDM) and Selective Laser Sintering (SLS), wherein, SLS printing cost is high, and the method is mainly used for printing and forming of some small-sized and high-precision TPU material parts, and FDM is simple in operation, low in equipment cost, and wide in raw materials, so that FDM is more suitable for printing and forming of large-sized parts by using TPU materials.
In the chinese patent document CN113493603A, "a heat-resistant polyurethane material for 3D printing and a method for making the same and a printing method thereof", a heat-resistant polyurethane material is prepared by blending talc powder and a p-phenylene diisocyanate based thermoplastic polyurethane elastomer, and is used for large-size non-pneumatic tire integrated 3D printing molding. However, the difficulty of the above method is that it is difficult to ensure that the talc powder is uniformly dispersed in the TPU resin system during blending, which causes unstable resin flow during printing of the blended resin, thereby affecting the product quality.
When the FDM technology is used for feeding, pressure is generated through opposite rotation of the feeding gears, then materials are fed into the melt tank, and the materials are sprayed out through the printing nozzle after being heated and melted in the melt tank, so that 3D printing is achieved. The raw materials used for printing need to have certain temperature resistance in a feeding pipe, and the molten resin has certain melt strength, so that two wheels can generate large traction force, and in addition, when the resin is extruded from a printing nozzle, the resin needs to have good fluidity, so that high-precision printing is realized.
At present, the types of thermoplastic polyurethane resin materials specially used for 3D printing and forming on the market are relatively few, and most of the thermoplastic polyurethane resin materials used for 3D printing are applied to 3D printing after the thermoplastic polyurethane materials of mature grades on the market are subjected to physical blending modification. The blending modification has no uniform specification, and the performance of printed products is difficult to maintain consistent.
Disclosure of Invention
In order to solve the problems, the invention provides an organic silicon modified thermoplastic polyurethane resin for 3D printing, which improves the temperature resistance of the polyurethane resin and the mechanical strength of a melt, thereby ensuring the feeding stability during 3D printing and having good mechanical properties and better melt flowability. The invention also provides a scientific and reasonable preparation method.
The organic silicon modified thermoplastic polyurethane resin for 3D printing comprises a component A and a component B, wherein the component A is an-OH end-capped polyurethane prepolymer prepared by the reaction of polyol and isocyanate, and the R value is 0.95 to 0.98;
the component B comprises-NCO end-blocked organosilane and a catalyst;
the molar ratio of-OH in the component A to-NCO in the component B is 1.
The polyol is a polyglycol.
The polyglycol is one or two of polyester diol and polyether diol.
The polyhydric alcohol comprises one or more of polycaprolactone diol, polycarbonate diol, polybutylene adipate diol, polyethylene adipate diol and polytetrahydrofuran ether diol.
The isocyanate includes one or more of diphenylmethane diisocyanate (MDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI).
the-NCO blocked organosilane includes one or more of isocyanatopropyltrimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropylmethyldimethoxysilane and isocyanatopropylmethyldiethoxysilane.
The catalyst comprises one or more of triethanolamine, N-dimethylethanolamine and N, N' -dimethylpyridine.
From the viewpoint of adjusting the molecular chain structure of the polyurethane resin and further changing the processing characteristics, the invention focuses on introducing a small-molecular organosilicon auxiliary agent, and searching the balance state of the melt mechanical strength and the processing fluidity of the thermoplastic polyurethane by adjusting the R value (namely the isocyanate index and the molar ratio of isocyanate group-NCO to hydroxyl group-OH) of the thermoplastic polyurethane and changing the using amount of isocyanate. The flow characteristic of the thermoplastic polyurethane elastomer material after melting is greatly related to the structure of the resin, isocyanate and a chain extender which are used as a hard segment part in a chain segment mainly contribute to the hardness index of the polyurethane resin and influence the processing fluidity of the resin after melting, and after an organic silicon chain segment is introduced into the polyurethane resin chain segment, the temperature resistance and the mechanical property of the polyurethane resin can be obviously improved. In summary, the invention develops an organic silicon modified thermoplastic polyurethane resin material which has higher melt strength and good processing fluidity and is used for 3D printing. The reaction mechanism of the invention is as follows:
the invention relates to a preparation method of organic silicon modified thermoplastic polyurethane resin for 3D printing, which comprises the following steps:
(1) Carrying out vacuum dehydration on polyol at the temperature of 110 to 120 ℃ for 1 to 2h, cooling to 70 to 75 ℃, then keeping the vacuum state, dripping isocyanate into a constant-pressure dripping funnel for 1.5 to 2.5h, and reacting for 2 to 3h after dripping to obtain a component A;
(2) mixing-NCO end-capped organosilane with a catalyst to obtain a component B;
(3) And (3) uniformly mixing the component A and the component B, heating to 80-120 ℃, and keeping for 0.5-2h to obtain the composition.
Compared with the prior art, the invention has the beneficial effects that:
1. due to the introduction of the organic silicon chain segment, the temperature resistance of polyurethane resin can be improved, so that the melt strength of thermoplastic polyurethane during 3D printing is improved, the thermoplastic polyurethane resin is prevented from being broken under the action of pressure generated by opposite rotation of a feeding gear of a 3D printer, and the stability of feeding is further ensured;
2. the organic silicon chain segment introduced in the invention adopts-NCO end capping organic silane, and the thermoplastic polyurethane resin obtained by the reaction of-NCO of the organic silane and the excessive-OH polyurethane prepolymer has higher mechanical property compared with the polyurethane resin without the organic silicon chain segment introduced, in addition, the flexibility of the organic silicon chain segment is better, so that the modified thermoplastic polyurethane resin has better melt fluidity;
3. the preparation of the organic silicon modified thermoplastic polyurethane resin belongs to chemical modification, and compared with physical modification, the condition of uneven dispersion does not exist, and the stability of the product quality is ensured to a great extent.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the following examples.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
Example 1
Preparing a component A: firstly, 500g of polycarbonate diol (hydroxyl value is 55mgKOH/g, number average molecular weight is 2040), the four-neck flask is heated to 120 ℃, the vacuum degree is kept at-0.1 MPa, the four-neck flask is continuously stirred for 1.5h to complete the vacuum dehydration of the polycarbonate diol, then the temperature is cooled to 70 ℃, 39.1g of hexamethylene diisocyanate is slowly added through the constant-pressure dropping funnel (the adding amount of the hexamethylene diisocyanate is calculated according to R = 0.95), the addition is completed in 1.5h, and the reaction is carried out for 2h, so that the-OH-terminated polyurethane prepolymer can be obtained;
preparing a component B: 5.06g of isocyanatopropyl trimethoxy silane and 2.53g of triethanolamine are uniformly mixed, wherein the using amount of the isocyanatopropyl trimethoxy silane is calculated according to the molar ratio of-OH in the component A to-NCO in the isocyanatopropyl trimethoxy silane as 1;
and (3) uniformly stirring the component A and the component B, heating to 90 ℃, and keeping stirring for 1.5 hours to obtain the organic silicon modified thermoplastic polyurethane resin for 3D printing.
Example 2
Preparing a component A: firstly, 500g of polydiethylene adipate glycol (hydroxyl value is 55mgKOH/g, number average molecular weight is 2040) is added into a four-neck flask provided with a polytetrafluoroethylene stirring paddle, a constant pressure dropping funnel, a serpentine condenser tube and nitrogen protection, the four-neck flask is heated to 120 ℃, the vacuum degree is kept at-0.1 MPa, the four-neck flask is continuously stirred for 1h to finish the vacuum dehydration of the polydiethylene adipate glycol, then the temperature is cooled to 75 ℃, 58.8g of diphenylmethane diisocyanate (the adding amount of the diphenylmethane diisocyanate is calculated according to R = 0.96) is slowly added through the constant pressure dropping funnel, the reaction is finished within 1.5h, and the-OH end-capped polyurethane prepolymer can be obtained after 2h reaction;
preparing a component B: 4.89g of isocyanatopropyl triethoxysilane and 2.45gN, N-dimethylethanolamine are uniformly mixed, wherein the usage amount of the isocyanatopropyl triethoxysilane is calculated according to the molar ratio of-OH in the component A to-NCO in the isocyanatopropyl triethoxysilane of 1;
and (3) uniformly stirring the component A and the component B, heating to 90 ℃, and keeping stirring for 2h to obtain the organic silicon modified thermoplastic polyurethane resin for 3D printing.
Example 3
Preparing a component A: firstly, 600g of polytetrahydrofuran ether glycol (hydroxyl value is 55mgKOH/g, number average molecular weight is 2040) is added into a four-neck flask provided with a polytetrafluoroethylene stirring paddle, a constant pressure dropping funnel, a serpentine condenser tube and nitrogen protection, the four-neck flask is heated to 100 ℃, the vacuum degree is kept at-0.3 MPa, the four-neck flask is continuously stirred for 2 hours to finish vacuum dehydration of the polytetrahydrofuran ether glycol, then the temperature is cooled to 70 ℃, 49.6g of toluene diisocyanate is slowly added into the four-neck flask through the constant pressure dropping funnel (the adding amount of the toluene diisocyanate is calculated according to R = 0.97), the addition is finished in 2 hours, and the reaction is carried out for 3 hours to obtain an-OH end-capped polyurethane prepolymer;
preparing a component B: 3.42g of isocyanate propyl methyl dimethoxy silane and 1.71g of triethanolamine are uniformly mixed, wherein the usage amount of the isocyanate propyl methyl dimethoxy silane is calculated according to the molar ratio of-OH content in the component A to-NCO in the isocyanate propyl methyl dimethoxy silane being 1;
and (3) uniformly stirring the component A and the component B, heating to 110 ℃, and keeping stirring for 0.5h to obtain the organic silicon modified thermoplastic polyurethane resin for 3D printing.
Example 4
Preparing a component A: firstly, 600g of polycaprolactone diol (hydroxyl value is 70mgKOH/g, number average molecular weight is 1600) is added into a four-neck flask provided with a polytetrafluoroethylene stirring paddle, a constant pressure dropping funnel, a snake-shaped condenser pipe and nitrogen protection, the four-neck flask is heated to 110 ℃, the vacuum degree is kept at-0.1 MPa, the four-neck flask is continuously stirred for 1h to finish the vacuum dehydration of the polycaprolactone diol, then the temperature is cooled to 70 ℃, 81.6g of isophorone diisocyanate (the adding amount of the isophorone diisocyanate is calculated according to R = 0.98) is slowly added through the constant pressure dropping funnel, the addition is finished within 2.5h, and the reaction is carried out for 3h, so that an-OH end-capped polyurethane prepolymer can be obtained;
preparing a component B: 3.23g of isocyanatopropylmethyldiethoxysilane and 1.62g of N, N' -dimethylpyridine are mixed uniformly, wherein the usage amount of the isocyanatopropylmethyldiethoxysilane is calculated according to the molar ratio of-OH in the component A to-NCO in the isocyanatopropylmethyldiethoxysilane being 1;
and (3) uniformly stirring the component A and the component B, heating to 100 ℃, and keeping stirring for 1.5 hours to obtain the organic silicon modified thermoplastic polyurethane resin for 3D printing.
Example 5
Preparing a component A: firstly, 500g of polybutylene adipate glycol (hydroxyl value is 55mgKOH/g, number average molecular weight is 2040) is added into a four-neck flask provided with a polytetrafluoroethylene stirring paddle, a constant pressure dropping funnel, a serpentine condenser tube and nitrogen protection, the four-neck flask is heated to 120 ℃, the vacuum degree is kept at-0.1 MPa, the four-neck flask is continuously stirred for 1h to finish vacuum dehydration of the polybutylene adipate glycol, then the temperature is cooled to 75 ℃, 40.9g of toluene diisocyanate (the adding amount of the toluene diisocyanate is calculated according to R = 0.96) is slowly added through the constant pressure dropping funnel, the addition is finished in 1.5h, and the reaction is carried out for 2h to obtain an-OH end-capped polyurethane prepolymer;
preparing a component B: 4.97g of isocyanatopropyl triethoxysilane and 2.49g of N, N-dimethylethanolamine are uniformly mixed, wherein the usage amount of the isocyanatopropyl triethoxysilane is calculated according to the molar ratio of-OH in the component A to-NCO in the isocyanatopropyl triethoxysilane of 1;
and (3) uniformly stirring the component A and the component B, heating to 100 ℃, and keeping stirring for 1h to obtain the organic silicon modified thermoplastic polyurethane resin for 3D printing.
Comparative example 1
Preparing a component A: firstly, 600g of polytetrahydrofuran ether glycol (hydroxyl value is 55mgKOH/g, number average molecular weight is 2040) is added into a four-neck flask provided with a polytetrafluoroethylene stirring paddle, a constant pressure dropping funnel, a serpentine condenser tube and nitrogen protection, the four-neck flask is heated to 115 ℃, the vacuum degree is kept at-0.1 MPa, the four-neck flask is continuously stirred for 2 hours to finish vacuum dehydration of the polytetrahydrofuran ether glycol, then the temperature is cooled to 75 ℃, 69.9g of diphenylmethane diisocyanate (the adding amount of the diphenylmethane diisocyanate is calculated according to R = 0.95) is slowly added into the four-neck flask through the constant pressure dropping funnel, the 1.5 hours of the polytetrahydrofuran ether glycol are added, and the reaction is finished for 2 hours, so that an-OH end-capped polyurethane prepolymer can be obtained;
preparing a component B: 10.64g of triphenylmethane triisocyanate, wherein the usage amount of the triphenylmethane triisocyanate is calculated according to the molar ratio of-OH in the component A to-NCO in the triphenylmethane triisocyanate of 1;
and (3) uniformly stirring the component A and the component B, heating to 120 ℃, and keeping stirring for 2 hours to obtain the thermoplastic polyurethane resin.
Comparative example 2
Preparing a component A: firstly, 600g of polytetrahydrofuran ether glycol (hydroxyl value is 70mgKOH/g, number average molecular weight is 1600) is added into a four-neck flask provided with a polytetrafluoroethylene stirring paddle, a constant pressure dropping funnel, a serpentine condenser tube and nitrogen protection, the four-neck flask is heated to 120 ℃, the vacuum degree is kept at-0.1 MPa, the four-neck flask is continuously stirred for 2h to finish the vacuum dehydration of the polytetrahydrofuran ether glycol, then the temperature is cooled to 70 ℃, 62.64g of toluene diisocyanate (the adding amount of the toluene diisocyanate is calculated according to R = 0.96) is slowly added into the four-neck flask through the constant pressure dropping funnel for 2h, and the reaction is carried out for 2h to obtain an-OH end-capped polyurethane prepolymer;
preparing a component B: 11.01g of triphenylmethane triisocyanate, wherein the usage amount of the triphenylmethane triisocyanate is calculated according to the molar ratio of-OH in the component A to-NCO in the triphenylmethane triisocyanate of 1;
and (3) uniformly stirring the component A and the component B, heating to 110 ℃, and keeping stirring for 1.5 hours to obtain the thermoplastic polyurethane resin.
Performance testing
The polyurethane materials prepared in examples 1 to 5 and comparative examples 1 to 2 were tabletted, the mechanical properties of the materials were tested, and the melt strength of the polyurethane materials was characterized by a melt flow rate tester, and the test results are shown in table 1.
The melt strength test specifically comprises: the mass of the melt during the time from suspension from the die of the melt flow rate meter to rupture was characterized by the fact that the melt was held at 224 ℃ in a barrel for 6min, fully extruded from the capillary with a weight of 8.7kg, while a small portion of the melt was suspended at the exit of the die, the time from the exit of the melt to rupture was recorded, the mass of the rupture was weighed and tested 4 times for each sample, and the mass of the extrudate suspended at the exit of the die for 10min was calculated by interpolation, the higher the mass of the extrudate, the higher the melt strength of the resin.
The test for the shore hardness (shore a) of the material is performed with reference to GB/T531-1999, and the test for the mechanical properties of the material is performed with reference to GB/T528-2009.
TABLE 1 Performance test tables for examples 1 to 5 and comparative examples 1 to 2
As can be seen from the table, the test results of the comparative examples 1 to 5 and the comparative examples 1 to 2 show that the mechanical property of the polyurethane resin is effectively improved by introducing the micromolecule-NCO end-blocked organosilane, and the tensile strength and the elongation at break of the polyurethane resin are obviously improved; due to the fact that the flexibility of the introduced organic silicon chain segment is particularly good, the thermoplastic polyurethane resin modified by the small-molecule organic silane has higher melt strength in a melt state.
From the test results of example 2 and example 5, it can be seen that the polyurethane resin prepared using diisocyanate having benzene ring and polyester diol has higher hardness value.
Claims (8)
1. An organic silicon modified thermoplastic polyurethane resin for 3D printing is characterized by comprising a component A and a component B, wherein the component A is an-OH end-capped polyurethane prepolymer prepared by the reaction of polyol and isocyanate, and the R value is 0.95 to 0.98;
the component B comprises-NCO end-blocked organosilane and a catalyst;
the molar ratio of-OH in the component A to-NCO in the component B is 1.
2. The silicone-modified thermoplastic polyurethane resin for 3D printing according to claim 1, wherein the polyol is a polyglycol.
3. The silicone-modified thermoplastic polyurethane resin for 3D printing according to claim 2, wherein the polyglycol is one or both of polyester glycol and polyether glycol.
4. The silicone-modified thermoplastic polyurethane resin for 3D printing according to claim 2, wherein the polyol comprises one or more of polycaprolactone diol, polycarbonate diol, polybutylene adipate diol, polyethylene adipate diol, and polytetrahydrofuran ether diol.
5. The silicone-modified thermoplastic polyurethane resin for 3D printing according to claim 1, wherein the isocyanate comprises one or more of diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
6. The silicone-modified thermoplastic polyurethane resin for 3D printing according to claim 1, wherein-NCO-blocked organosilane comprises one or more of isocyanatopropyltrimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropylmethyldimethoxysilane, and isocyanatopropylmethyldiethoxysilane.
7. The silicone-modified thermoplastic polyurethane resin for 3D printing according to claim 1, wherein the catalyst comprises one or more of triethanolamine, N-dimethylethanolamine, and N, N' -dimethylpyridine.
8. A method for preparing the organic silicon modified thermoplastic polyurethane resin for 3D printing according to any one of claims 1 to 7, which is characterized by comprising the following steps:
(1) Dehydrating the polyol at 110-120 ℃ in vacuum for 1-2h, cooling to 70-75 ℃, keeping the vacuum state, dripping isocyanate into the polyol by using a constant-pressure dropping funnel for 1.5-2.5 h, and reacting for 2-3h after dripping to obtain a component A;
(2) mixing-NCO end-capped organosilane with a catalyst to obtain a component B;
(3) And (3) uniformly mixing the component A and the component B, heating to 80-120 ℃, and keeping for 0.5-2h to obtain the composition.
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| US20200055976A1 (en) * | 2016-11-17 | 2020-02-20 | Mitsui Chemicals, Inc. | Producing method of polyurethane resin, polyurethane resin, and molded article |
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