CN111471152A - Polymer compound and manufacturing method thereof, waterproof adhesive material and lamp - Google Patents
Polymer compound and manufacturing method thereof, waterproof adhesive material and lamp Download PDFInfo
- Publication number
- CN111471152A CN111471152A CN201910061934.9A CN201910061934A CN111471152A CN 111471152 A CN111471152 A CN 111471152A CN 201910061934 A CN201910061934 A CN 201910061934A CN 111471152 A CN111471152 A CN 111471152A
- Authority
- CN
- China
- Prior art keywords
- formula
- represented
- polymer compound
- positive integer
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3844—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring
- C08G18/3846—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring containing imide groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V31/00—Gas-tight or water-tight arrangements
- F21V31/005—Sealing arrangements therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a high molecular compound, a manufacturing method thereof, a waterproof adhesive material and a lamp. The polymer compound is represented by the following formula 1. The polymer compound has good adhesion, stain resistance, weather resistance, hydrolysis resistance and easy processability.
Description
Technical Field
The present invention relates to a compound, and more particularly to a polymer compound, a method for producing the same, a waterproof adhesive material, and a lamp.
Background
Generally, the conventional waterproof strip or sealant is made of silicone, which can be used to seal the device, and further isolate moisture to protect the device. However, the conventional waterproof tape using silicone rubber as a material has the following disadvantages: the waterproof adhesive tape is easy to accumulate dirt and dust, and poor in adhesion and weather resistance due to poor elasticity. Taking a lamp as an example, when the waterproof effect of the waterproof rubber strip is not good, moisture easily enters the lamp, and the situations such as circuit short circuit and the like occur.
In addition, Thermoplastic Polyurethane (TPU) is a functional elastomer whose properties include abrasion resistance, shock absorption, flexibility, elasticity and chemical resistance, and thus can also be used to make a waterproof strip. However, conventional TPUs typically use polyesters as the soft segment, which are not resistant to hydrolysis, reducing the durability of the material.
Disclosure of Invention
The present invention provides a polymer compound having excellent adhesion, stain resistance, weather resistance, hydrolysis resistance and workability.
The invention provides a method for producing a polymer compound, which can produce a polymer compound having excellent physical properties.
The invention provides a waterproof adhesive material which has good adhesion, stain resistance, weather resistance, hydrolysis resistance and easy processability.
The invention provides a lamp which has better waterproofness.
The polymer compound of the present invention is represented by formula 1:
in formula 1, R1Is composed of
R2Represented by formula 2-1 or formula 2-2, n is a positive integer of 18 or less, m is a positive integer of 25 or less, x is a positive integer of 45 or less,
in the formula 2-1, a is 0 or 1,
in the formula 2-2, b is a positive integer of 3 to 6,
a is represented by formula 3-1 or formula 3-2,
R3is- (CH)2)c-, c is a positive integer of 6 or less,
in an embodiment of the present invention, a in the polymer compound is represented by formula 3-1, and the molecular weight of the polymer compound may be 20,000 to 84,000.
In an embodiment of the invention, a in the polymer compound is represented by formula 3-2, and the molecular weight of the polymer compound may be 14,000 to 76,000.
The method for producing a polymer compound of the present invention comprises reacting OCN-R1Compounds represented by-NCO and by HO-R2Polymerizing a compound represented by-OH to form a polymer represented by formula 4,
in formula 4, R1Is composed of
R2Represented by formula 2-1 or formula 2-2, n is a positive integer of 18 or less, m is a positive integer of 25 or less,
in the formula 2-1, a is 0 or 1,
in formula 2-2, b is a positive integer of 3 to 6.
In an embodiment of the present invention, the OCN-R in the above manufacturing method1-NCO：HO-R2The ratio of-OH can be 1:1 to 2: 1.
in an embodiment of the invention, the above R2Represented by formula 2-1, and made of HO-R2The step of the compound represented by-OH comprises reacting phthalic anhydride with the compound represented by formula 5-1,
a is 0 or 1.
In an embodiment of the invention, the above R2Represented by formula 2-2, and made by HO-R2-OH comprising the steps of: reacting 2,6-pyridinedimethanol (2,6-pyridinedimethanol) with a compound represented by formula 5-2,
HOOC-(CF2)b-HOOC formula 5-2
b is a positive integer from 3 to 6.
In an embodiment of the present invention, the above-mentioned method further comprises subjecting the polymer represented by formula 4 to a chain extension reaction or a curing reaction to form a polymer compound represented by formula 1,
in formula 1, R1Is composed of
R2Represented by formula 2-1 or formula2-2 represents n is a positive integer of 18 or less, m is a positive integer of 25 or less, x is a positive integer of 45 or less,
in the formula 2-1, a is 0 or 1,
in the formula 2-2, b is a positive integer of 3 to 6,
a is represented by formula 3-1 or formula 3-2,
R3is- (CH)2)c-, c is a positive integer of 6 or less,
in one embodiment of the present invention, the chain extension reaction includes reacting the polymer represented by formula 4 with HO-R3-OH, wherein A in the resulting polymer compound is represented by formula 3-1.
In an embodiment of the present invention, the OCN-R in the above manufacturing method1-NCO：HO-R2-OH：HO-R3-OH ratio of 4:3.5:0.5 to 4:2: 2.
in an embodiment of the present invention, the curing reaction includes reacting the polymer represented by formula 4 with moisture, wherein a in the resulting polymer compound is represented by formula 3-2.
The waterproof adhesive material comprises the macromolecular compound.
The lamp comprises a lampshade, a base and the waterproof adhesive material, wherein the waterproof adhesive material is arranged at the combination position of the base and the lampshade.
The polymer compound of the present invention has a hard segment including an aromatic group, an aliphatic group or a combination thereof, and a soft segment including a group represented by formula 2-1 or formula 2-2:
in the formula 2-1, a is 0 or 1,
in formula 2-2, b is a positive integer of 3 to 6.
In an embodiment of the present invention, the aromatic group of the hard segment may include a benzene ring, a bis-benzene ring, pyridine, bis-pyridine, pyran or six-membered ring heterocyclic structure. The aliphatic group of the hard segment may include alicyclic, olefinic, paraffinic, ether, ketone or ester. In the hard-segment aliphatic, the pendant side groups on the alkane may also include elements such as oxygen, nitrogen, or sulfur.
In view of the above, the polymer compound provided by the present invention is a compound represented by formula 1, and thus has excellent adhesion, stain resistance, weather resistance, hydrolysis resistance, and easy processability. In addition, the method for producing the polymer compound provided by the invention can produce the polymer compound with better physical properties. In addition, the waterproof adhesive material provided by the invention is made of a high molecular compound, so that the waterproof adhesive material has better adhesion, stain resistance, weather resistance, hydrolysis resistance and easy processability. On the other hand, in the lamp provided by the invention, the waterproof adhesive material is arranged at the combination position of the base and the lampshade, so that the waterproofness of the lamp can be improved, the phenomenon that a circuit is short-circuited due to moisture entering the lamp is prevented, and the durability of the lamp is improved.
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below.
Drawings
Fig. 1 is a schematic view of a lamp according to an embodiment of the invention.
Fig. 2 is a partially enlarged view of fig. 1.
[ notation ] to show
100: lamp shade
200: base seat
300: waterproof glue material
Detailed Description
In this context, a range of values from one value to another is a general expression avoiding any recitation of all values in the range in the specification. Thus, recitation of a range of values herein is intended to encompass any value within the range and any smaller range defined by any value within the range, as if the range and smaller range were explicitly recited in the specification.
Herein, the structure of a compound or group is sometimes represented by a bond line type (skeletton formula). This notation may omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. Of course, the drawing is to be understood as referring to the atoms or atom groups explicitly depicted in the structural formula.
When groups are represented herein as bonded, they are represented as wavy lines
To indicate the position of linkage of the group to other compounds or groups.
One embodiment of the present invention provides a polymer compound represented by the following formula 1, which is a Thermoplastic Polyurethane (TPU). In some embodiments, the hard segment of the polymeric compound comprises an aromatic group, an aliphatic group, or a combination thereof (e.g., R)1And the soft segment of the above-mentioned polymer compound includes a group represented by formula 2-1 or formula 2-2. The aromatic group of the hard segment may include a benzene ring, a bis-benzene ring, pyridine, bis-pyridine, pyran or a six-membered ring heterocyclic structure. The aliphatic group of the hard segment may include alicyclic, olefinic, paraffinic, ether, ketone or ester. In the hard-segment aliphatic, the pendant side groups on the alkane may also include elements such as oxygen, nitrogen, or sulfur.
In formula 1, R1Is composed of
In formula 1, R2Represented by formula 2-1 or formula 2-2.
In the formula 2-1, a is 0 or 1. Since the soft segment in the polymer compound of this embodiment has the group represented by formula 2-1, the polymer compound has better hydrolysis resistance and a sharp phase transition temperature transition point, so that the polymer compound can be processed and molded more easily.
In formula 2-2, b is a positive integer of 3 to 6. Since the soft segment in the polymer compound of this embodiment has the group represented by formula 2-2, it has better shape-recovering property, and further, it can achieve the characteristics of easy processing and reuse, and solves the problems of easy hydrolysis and weak durability of the conventional TPU, and further solves the problems of easy fouling and incapability of reuse of the silica gel used in the current lamp.
In formula 1, n is a positive integer of 18 or less, m is a positive integer of 25 or less, and x is a positive integer of 45 or less.
In some embodiments of the invention, A may be represented by formula 3-1 or formula 3-2. When a is represented by formula 3-1, the molecular weight of the high molecular compound represented by formula 1 may range from 20,000 to 84,000. When a is represented by formula 3-2, the molecular weight of the high molecular compound represented by formula 1 may range from 14,000 to 76,000.
In some embodiments of the invention, R3Is- (CH)2)c-, c is a positive integer of 6 or less. In other words, R3Can be methylene or linear alkylene with carbon number less than 6. R3The number of carbon atoms of (A) is limited, for example, R3The number of carbon (C) is preferably not more than 6, and when the number of carbon (C) exceeds 6, the molecular arrangement of the polymer compound is disturbed or the reactivity is deteriorated, resulting in deterioration of the physical properties of the polymer compound.
In addition, A in formula 1 can extend the length of the polymer compound and increase the molecular weight thereof, thereby further improving physical properties (e.g., mechanical strength and heat resistance).
In some embodiments, R in formula 12When A is represented by the formula 2-1 and A is represented by the formula 3-1, n is a positive integer of 12 or less, m is a positive integer of 22 or less, and x is a positive integer of 38 or less. R in formula 12When A is represented by the formula 2-1 and A is represented by the formula 3-2, n is a positive integer of 12 or less, m is a positive integer of 22 or less, and x is a positive integer of 30 or less. R in formula 12When A is represented by the formula 2-2 and A is represented by the formula 3-1, n is a positive integer of 18 or less, m is a positive integer of 25 or less, and x is a positive integer of 45 or less. R in formula 12When A is represented by the formula 2-2 and A is represented by the formula 3-2, n is a positive integer of 18 or less, m is a positive integer of 25 or less, and x is a positive integer of 36 or less.
As can be seen from the above, the polymer compound of the above example is a compound represented by formula 1, and thus has preferable adhesion, stain resistance, weather resistance, hydrolysis resistance, and easy processability.
< manufacturing method >
In one embodiment of the present invention, a method for producing a polymer compound includes: from HO-R2A compound represented by-OH and represented by OCN-R1The compound represented by-NCO is subjected to polymerization reaction to form a polymer represented by formula 4. The polymerization reaction can be carried out in an atmosphere of nitrogen gas. However, the present invention is not limited thereto. Of reactionThe temperature may be 70 to 90 degrees celsius. The reaction is carried out by stirring with a mechanical stirrer at a speed of 100 to 300 rpm. The reaction time may be 1 hour to 3 hours.
In formula 4, R1Is composed of
n is a positive integer of 18 or less, and m is a positive integer of 25 or less.
R2Represented by formula 2-1 or formula 2-2.
In the formula 2-1, a is 0 or 1.
In formula 2-2, b is a positive integer of 3 to 6.
In some embodiments of the invention, R2Represented by formula 2-1, and HO-R2-OH can be synthesized by: phthalic anhydride was polymerized with the compound represented by formula 5-1. The conditions for the above polymerization reaction include polymerization under an atmosphere of nitrogen gas. However, the present invention is not limited thereto as long as the introduced gas does not participate in the reaction performed in the production of the polymer compound. In one embodiment, the reaction time may be 12 hours. The reaction time can also be adjusted according to actual needs. The molar ratio of phthalic anhydride to the compound represented by formula 5-1 may be 1:1, but not limited thereto.
a is 0 or 1.
In some embodiments of the invention, R2Represented by formula 2-2, and HO-R2-OH can be synthesized by: reacting 2,6-pyridinedimethanol with a compound represented by formula 5-2. In addition, dibutyltin oxide (dibutyl tin oxide) may be added as a reaction auxiliary in the above reaction. The conditions for the above polymerization reaction include polymerization under an atmosphere of nitrogen gas. However, the present invention is not limited thereto as long as the introduced gas does not participate in the reaction performed in the production of the polymer compound. In one embodiment, the reaction time may be 12 hours, and the reaction temperature may be 200 ℃. The reaction time and the reaction temperature can also be adjusted according to actual needs. The molar ratio of 2,6-pyridinedimethanol to the compound represented by formula 5-2 may be 1:1, but not limited thereto.
HOOC-(CF2)b-HOOC formula 5-2
b is a positive integer from 3 to 6.
In one embodiment, the polymer is synthesized by reacting HO-R2-OH and OCN-R1the-NCO is stirred and reacted in the environment of nitrogen gas, wherein the OCN-R1-NCO and HO-R2The molar ratio of-OH may be from 1:1 to 2: 1.
The method for producing the polymer compound further includes subjecting the polymer represented by formula 4 to a chain extension reaction to form the polymer compound represented by formula 1. The chain extension reaction includes reacting the polymer represented by formula 4 with HO-R3-OH (chain extender) reaction. For example, after the polymer represented by formula 4 is formed, the polymer represented by formula 4 is reacted with HO-R3The reaction of-OH in the reaction vessel is continued for 1 hour to 3 hours (e.g., 2 hours). In this embodiment, A in the polymer compound represented by formula 1 obtained by the above-mentioned chain extension reaction may be-O-R3-O-。OCN-R1-NCO：HO-R2-OH：HO-R3-OH ratio of 4:3.5:0.5 to 4:2: 2. for example, OCN-R1-NCO、HO-R2-OH and HO-R3The molar ratio of-OH may be 4:3.5:0.5, 4:3:1, 4:2.5:1.5, 4:2:2, but the present invention is not limited thereto.
In some embodiments, the polymer represented by formula 4 is subjected to a curing reaction to form a high molecular compound represented by formula 1. The curing reaction is to react the polymer with moisture. For example, the polymer may be left in an environment with a relative humidity of 45% or more for 6 hours to 24 hours (e.g., at a relative humidity of 80%, for 6 hours) to react the polymer with H in the air2And (4) reacting. In this embodiment, a in the polymer compound represented by formula 1 obtained through the above curing reaction may be an oxy group.
In some embodiments, the molecular weight of the high molecular compound obtained by the chain extension reaction may be greater than the molecular weight of the high molecular compound obtained by the curing reaction. For example, the molecular weight of the high molecular compound obtained by the chain extension reaction may range from 20,000 to 84,000. In the curing reaction, the molecular weight of the high molecular compound obtained by the curing reaction may range from 14,000 to 76,000.
In addition, in order to carry out the chain extension reaction or the curing reaction, the reaction is carried out by HO-R2A compound represented by-OH and represented by OCN-R1In the polymerization of the compound represented by-NCO, OCN-R is used1-NCO. Thus, in the chain extension reaction or curing reaction, the NCO groups at both ends of the polymer represented by formula 4, OCN-R1-NCO and HO-R3the-OH groups will react, causing further extension of the main chain of the polymer.
In some embodiments, the method of manufacturing the polymer compound may not perform the chain extension reaction or the curing reaction. In other words, the reaction may be terminated after the aforementioned polymer represented by formula 4 is obtained.
As can be seen from the above, the method for producing a polymer compound according to the above example can produce a polymer compound having preferable physical properties.
In addition, in an embodiment of the present invention, the waterproof adhesive material includes the polymer compound, so that the waterproof adhesive material has better adhesion, stain resistance, weather resistance, hydrolysis resistance and easy processability. Therefore, the waterproof adhesive material of the embodiment solves the defects that the traditional polyester TPU is easy to hydrolyze and is not durable, and the problems that silica gel used by the existing lamp is easy to accumulate dirt, poor in weather resistance and poor in fitting performance.
Fig. 1 is a schematic view of a lamp according to an embodiment of the invention. Fig. 2 is a partially enlarged view of fig. 1.
Referring to fig. 1 and 2, the lamp includes a lamp cover 100, a base 200 and a waterproof adhesive material 300. The waterproof adhesive material 300 is disposed at a coupling position of the base 200 and the lamp cover 100. The waterproof adhesive material 300 may be a waterproof adhesive tape. The material of the waterproof adhesive material 300 is, for example, the polymer compound in the above embodiment.
As can be seen from the above, in the lamp of the above embodiment, the waterproof adhesive material 300 of the above embodiment is disposed at the joint position of the base 200 and the lampshade 100, so that the waterproof property of the lamp can be improved, the occurrence of a short circuit due to moisture entering the lamp can be prevented, and the durability of the lamp can be improved.
< Experimental example 1 >
< Synthesis of 2- (1,3-dihydroxy-2-methylpropan-2-yl) isoindole-1, 3-dione (2- (1,3-dihydroxy-2-methylpropan-2-yl) isoindoline-1,3-dione, DMID) >)
Phthalic anhydride represented by formula 6 and 2-amino-2-methyl-1, 3-propanediol represented by formula 7 (2-amino-2-methylpropane-1,3-diol) were added to a reaction vessel in a molar ratio of 1:1, and the reaction was stirred at room temperature for 12 hours under an atmosphere of nitrogen gas introduction, to finally obtain DMID represented by formula 8.
< Synthesis examples 1-1-1 to 1-4 >)
< Synthesis example 1-1-1 >)
1, 6-hexamethylene diisocyanate (1,6-Diisocyanatohexane, HDI) and DMID were initially introduced into a 500ml three-necked reaction flask and heated to 80 ℃ and mixed using a mechanical stirrer at 200 rpm. After 2 hours of reaction, a TPU polymer was formed. Then, 1,4-butanediol (1, 4-butaneediol) was added to the three-necked reaction flask and the chain extension reaction was continued for 2 hours, finally forming a chain-extended TPU polymer (highly crystalline polyurethane waterproofing strip). HDI in the reaction: DMID: the proportion of 1,4-butanediol is 4:3.5: 0.5.
< Synthesis examples 1-1-2 to 1-1-3 >)
Synthesis examples 1-1-2 and 1-1-3 were similar to the synthesis methods of Synthesis examples 1-1-1, with the difference that HDI of Synthesis examples 1-1-2 and 1-1-3: DMID: the proportion of 1,4-butanediol is respectively 4:3:1 and 4:2.5: 1.5.
< Synthesis examples 1-2-1 to 1-2-3 >
Synthesis examples 1-2-1 to 1-2-3 were similar to the synthesis methods of Synthesis examples 1-1-1 to 1-1-3, except that 1,4-butanediol was replaced with 1,5-pentanediol (1, 5-pentanediol).
< Synthesis examples 1-3-1 to 1-3-3 >)
Synthesis examples 1-3-1 to 1-3-3 were similar to the synthesis methods of Synthesis examples 1-1-1 to 1-1-3, except that 1,4-butanediol was replaced with 1,6-hexanediol (1, 6-hexanediol).
< Synthesis examples 1-4 >
Synthesis examples 1 to 4 were similar to the synthesis methods of Synthesis examples 1 to 1, with the following differences. In synthesis examples 1 to 4, HDI: the ratio of DMID was 4:3 and after forming the TPU polymer, no chain extender is added (i.e., no chain extension reaction is performed), but the TPU polymer is left in an environment having a relative humidity of 45% or more for 24 hours to be cured with moisture in the air to obtain a cured TPU polymer.
TABLE 1
In the above synthetic examples, the chain-extended TPU polymer has a molecular weight of 20,000 to 38,000, and the cured TPU polymer has a molecular weight of 14,000 to 20,000. The chain extended TPU polymers have better mechanical properties and thermal stability due to their higher molecular weight.
< Synthesis examples 2-1-1 to 2-4 >)
Synthetic examples 2-1-1 to 2-1-3, 2-2-1 to 2-2-3, 2-3-1 to 2-3-3, and 2-4 were synthesized in a similar manner to the synthetic examples 1-1-1 to 1-3, 1-2-1 to 1-2-3, 1-3-1 to 1-3-3, and 1-4, respectively, except that HDI was replaced with 4,4' -diphenylmethane diisocyanate (MDI).
TABLE 2
In the above synthetic examples, the chain-extended TPU polymer has a molecular weight of 26,000 to 41,000, and the cured TPU polymer has a molecular weight of 22,000 to 26,000. The chain extended TPU polymers have better mechanical properties and thermal stability due to their higher molecular weight.
< Synthesis examples 3-1-1 to 3-4 >)
Synthetic examples 3-1-1 to 3-1-3, 3-2-1 to 3-2-3, 3-3-1 to 3-3-3, and 3-4 were synthesized in a similar manner to the synthetic examples 1-1-1 to 1-3, 1-2-1 to 1-2-3, 1-3-1 to 1-3-3, and 1-4, respectively, except that HDI was replaced with toluene-2,4-diisocyanate (TDI).
TABLE 3
In the above synthetic examples, the chain-extended TPU polymer has a molecular weight of 28,000 to 43,000, and the cured TPU polymer has a molecular weight of 23,000 to 27,000. The chain extended TPU polymers have better mechanical properties and thermal stability due to their higher molecular weight.
< Synthesis examples 4-1-1 to 4-4 >)
Synthetic examples 4-1-1 to 4-1-3, 4-2-1 to 4-2-3, 4-3-1 to 4-3-3, and 4-4 were synthesized in a similar manner to the synthetic methods of synthetic examples 1-1-1 to 1-3, 1-2-1 to 1-2-3, 1-3-1 to 1-3-3, and 1-4, respectively, except that HDI was replaced with isophorone diisocyanate (IPDI).
TABLE 4
In the above synthetic examples, the chain-extended TPU polymer has a molecular weight of 23,000 to 39,000, and the cured TPU polymer has a molecular weight of 19,000 to 24,000. The chain extended TPU polymers have better mechanical properties and thermal stability due to their higher molecular weight.
< Synthesis examples 5-1-1 to 5-4 >)
Synthesis examples 5-1-1 to 5-1-3, 5-2-1 to 5-2-3, 5-3-1 to 5-3-3 and 5-4 were synthesized in a similar manner to the synthesis examples 1-1-1 to 1-3, 1-2-1 to 1-2-3, 1-3-1 to 1-3-3 and 1-4, respectively, except that HDI was replaced with 1-isocyanato-4- [ (4-isocyanatocyclohexyl) methyl group]Cyclohexane (1-isocyanato-4- [ (4-isocyanatoctyloxyl) methyl)]cyclohexane，H12MDI)。
TABLE 5
In the above synthetic examples, the chain-extended TPU polymer has a molecular weight of 25,000 to 36,000, and the cured TPU polymer has a molecular weight of 19,000 to 23,000. The chain extended TPU polymers have better mechanical properties and thermal stability due to their higher molecular weight.
< waterproof rubber strip >
The TPU polymers of synthetic examples 1-1-1 to 5-4 described above were formed into a weatherproof strip for testing. The test results show that the waterproof rubber strip produced by the above synthesis example has excellent physical properties (e.g., elasticity, water resistance, adhesion, stain resistance, weather resistance, hydrolysis resistance, easy processability, mechanical strength, heat resistance, yellowing resistance, etc.). In particular, the waterproof tape synthesized using HDI has excellent elasticity, the waterproof tape synthesized using MDI has excellent mechanical strength and heat resistance, and the waterproof tape synthesized using HDI or IPDI has excellent yellowing resistance and weather resistance.
< Experimental example 2 >
< Synthesis of perfluoropropane-1,3-diylbis (2- (6- (hydroxymethyl) pyridin-2-yl) acetate)) (perfluoropropane-1,3-diylbis (2- (6- (hydroxymethyl) pyridine-2-yl) acetate), PDHA) > (PDHA)
2,6-pyridinedimethanol represented by formula 9, 2,3,3,4, 4-hexafluoroglutaric acid (2,2,3,3,4, 4-hexafluoroglutaric acid) represented by formula 10 and dibutyltin oxide as a reaction auxiliary agent were added to a reaction vessel in a molar ratio of 2:1:1.2, and the reaction was stirred at 200 ℃ for 12 hours under a nitrogen-purged atmosphere, to finally obtain PDHA represented by formula 11.
< Synthesis example 6-1-1 to Synthesis example 10-4 >
< Synthesis example 6-1-1 >)
HDI and PDHA were initially charged in a 500ml three-necked reaction flask and heated to 80 ℃ and mixed using a mechanical stirrer at 200 rpm. After 2 hours of reaction, a TPU polymer was formed. Then, 1,4-butanediol was added to the three-necked reaction flask, and the chain extension reaction was continued for 2 hours, to finally form a chain-extended TPU polymer (fluorine-containing shape memory polyurethane waterproofing strip). HDI in the reaction: PDHA: the proportion of 1,4-butanediol is 4:3.5: 0.5.
< Synthesis examples 6-1-2 to 6-1-3 >
Synthesis examples 6-1-2 and 6-1-3 were similar to the synthesis method of Synthesis example 6-1-1, except that the HDI in Synthesis examples 6-1-2 and 6-1-3: PDHA: the proportion of 1,4-butanediol is respectively 4:3:1 and 4:2.5: 1.5.
< Synthesis examples 6-2-1 to 6-2-3 >
Synthesis examples 6-2-1 to 6-2-3 were similar to the synthesis methods of Synthesis examples 6-1-1 to 6-1-3, except that 1,4-butanediol was replaced with 1, 5-pentanediol.
< Synthesis examples 6-3-1 to 6-3-3 >)
Synthesis examples 6-3-1 to 6-3-3 were similar to the synthesis methods of Synthesis examples 6-1-1 to 6-1-3, except that 1,4-butanediol was replaced with 1, 6-hexanediol.
< Synthesis example 6-4 >
Synthesis example 6-4 was synthesized similarly to Synthesis example 6-1-1, with the following differences. In synthetic examples 6 to 4, HDI: the ratio of PDHA was 4:3 and after forming the TPU polymer, no chain extender is added (i.e., no chain extension reaction is performed), but the TPU polymer is left in an environment having a relative humidity of 45% or more for 24 hours to be cured with moisture in the air to obtain a cured TPU polymer.
TABLE 6
In the above synthetic examples, the chain-extended TPU polymer has a molecular weight of 41,000 to 52,000, and the cured TPU polymer has a molecular weight of 33,000 to 42,000. The chain extended TPU polymers have better mechanical properties and thermal stability due to their higher molecular weight.
< Synthesis examples 7-1-1 to 7-4 >)
Synthesis examples 7-1-1 to 7-1-3, 7-2-1 to 7-2-3, 7-3-1 to 7-3-3 and 7-4 were synthesized in a similar manner to the synthesis examples 6-1-1 to 6-1-3, 6-2-1 to 6-2-3, 6-3-1 to 6-3-3 and 6-4, respectively, except that HDI was replaced with MDI.
TABLE 7
In the above synthetic examples, the chain-extended TPU polymer has a molecular weight of 63,000 to 81,000, and the cured TPU polymer has a molecular weight of 57,000 to 72,000. The chain extended TPU polymers have better mechanical properties and thermal stability due to their higher molecular weight.
< Synthesis examples 8-1-1 to 8-4 >)
Synthesis examples 8-1-1 to 8-1-3, 8-2-1 to 8-2-3, 8-3-1 to 8-3-3 and 8-4 were synthesized in a similar manner to the synthesis examples 6-1-1 to 6-1-3, 6-2-1 to 6-2-3, 6-3-1 to 6-3-3 and 6-4, respectively, except that HDI was replaced with TDI.
TABLE 8
In the above synthetic examples, the chain-extended TPU polymer has a molecular weight of 68,000 to 84,000, and the cured TPU polymer has a molecular weight of 59,000 to 76,000. The chain extended TPU polymers have better mechanical properties and thermal stability due to their higher molecular weight.
< Synthesis examples 9-1-1 to 9-4 >)
Synthesis examples 9-1-1 to 9-1-3, 9-2-1 to 9-2-3, 9-3-1 to 9-3-3, and 9-4 were synthesized in a similar manner to the synthesis examples 6-1-1 to 6-1-3, 6-2-1 to 6-2-3, 6-3-1 to 6-3-3, and 6-4, respectively, except that HDI was replaced with IPDI.
TABLE 9
In the above synthetic examples, the chain-extended TPU polymer has a molecular weight of 54,000 to 68,000, and the cured TPU polymer has a molecular weight of 48,000 to 52,000. The chain extended TPU polymers have better mechanical properties and thermal stability due to their higher molecular weight.
< Synthesis examples 10-1-1 to 10-4 >)
Synthesis examples 10-1-1 to 10-1-3, 10-2-1 to 10-2-3, 10-3-1 to 10-3-3 and 10-4 were synthesized in the same manner as in Synthesis examples 6-1-1 to 6-1-3, 6-2-1 to 6-2-3, 6-3-1 to 6-3-3 and 6-4, respectively, except that HDI was replaced with H12HDI。
Watch 10
In the above synthetic examples, the chain-extended TPU polymer has a molecular weight of 36,000 to 68,000, and the cured TPU polymer has a molecular weight of 28,000 to 44,000. The chain extended TPU polymers have better mechanical properties and thermal stability due to their higher molecular weight.
< waterproof rubber strip >
The TPU polymers of synthetic examples 6-1-1 to 10-4 described above were formed into a weatherproof strip for testing. The test results showed that the water-resistant rubber strip produced in the above synthetic example exhibited excellent physical properties (e.g., elasticity, shape recovery, water resistance, adhesion, stain resistance, weather resistance, hydrolysis resistance, workability, mechanical strength, heat resistance, yellowing resistance, etc.). In particular, the waterproof stripe synthesized using HDI has excellent elasticity, the waterproof stripe synthesized using MDI has excellent mechanical strength and heat resistance, and H is used12The waterproof rubber strip synthesized by MDI or IPDI has excellent yellowing resistance and weather resistance. In terms of shape recovery, the waterproof rubber strip synthesized using HDI and the waterproof rubber strip synthesized using H are sequentially from the best to the worst12The waterproof rubber strip synthesized by MDI, the waterproof rubber strip synthesized by IPDI and the waterproof rubber strip synthesized by TDI. Furthermore, the shape recovery of the bead using IPDI is about 8% lower than that of the bead using MDI and is higher than that of the bead using H12MDI synthesized water-resistant strips were about 15% lower. The shape recovery of the strip using TDI was about 10% lower than that of the strip using IPDI.
As described above, the polymer compound (highly crystalline polyurethane) of the above example can have preferable physical properties. In addition, the method for producing a polymer compound according to the above embodiment can produce a polymer compound having preferable physical properties. In addition, the material of the waterproof adhesive material of the embodiment includes the polymer compound, so that the waterproof adhesive material has better physical properties. On the other hand, in the lamp of the above embodiment, the waterproof adhesive material is disposed at the joint position of the base and the lampshade, so that the waterproof property of the lamp can be improved, and the durability of the lamp can be improved.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (15)
1. A polymer compound, which is represented by formula 1:
in formula 1, R1Is composed of
R2Represented by formula 2-1 or formula 2-2, n is a positive integer of 18 or less, m is a positive integer of 25 or less, x is a positive integer of 45 or less,
in the formula 2-1, a is 0 or 1,
in the formula 2-2, b is a positive integer of 3 to 6,
a is represented by formula 3-1 or formula 3-2,
R3is- (CH)2)c-, c is a positive integer of 6 or less,
2. the polymer compound according to claim 1, wherein a is represented by formula 3-1, and the molecular weight of the polymer compound is 20,000 to 84,000.
3. The polymer compound according to claim 1, wherein a is represented by formula 3-2, and the molecular weight of the polymer compound is 14,000 to 76,000.
4. A method for producing a polymer compound, comprising:
by OCN-R1Compounds represented by-NCO and by HO-R2Polymerizing a compound represented by-OH to form a polymer represented by formula 4,
in formula 4, R1Is composed of
R2Represented by formula 2-1 or formula 2-2, n is a positive integer of 18 or less, m is a positive integer of 25 or less,
in the formula 2-1, a is 0 or 1,
in formula 2-2, b is a positive integer of 3 to 6.
5. A method for producing a polymer compound according to claim 4, wherein OCN-R1-NCO：HO-R2-OH ratio of 1:1 to 2: 1.
6. a method for producing a polymer compound according to claim 4, wherein R is2Represented by formula 2-1, and made of HO-R2-OH, comprising:
reacting phthalic anhydride with a compound represented by formula 5-1,
a is 0 or 1.
7. A method for producing a polymer compound according to claim 4, wherein R is2Represented by formula 2-2, and made by HO-R2-OH, comprising:
reacting 2,6-pyridinedimethanol with a compound represented by formula 5-2,
HOOC-(CF2)b-HOOC formula 5-2
b is a positive integer from 3 to 6.
8. The method for producing a polymer compound according to claim 4, further comprising subjecting the polymer represented by formula 4 to a chain extension reaction or a curing reaction to form a polymer compound represented by formula 1,
in formula 1, R1Is composed of
R2Represented by formula 2-1 or formula 2-2, n is a positive integer of 18 or less, m is a positive integer of 25 or less, x is a positive integer of 45 or less,
in the formula 2-1, a is 0 or 1,
in the formula 2-2, b is a positive integer of 3 to 6,
a is represented by formula 3-1 or formula 3-2,
R3is- (CH)2)c-, c is a positive integer of 6 or less,
9. the method for producing a polymer compound according to claim 8, wherein the chain extension reaction comprises:
reacting the polymer represented by formula 4 with HO-R3-OH reaction, wherein
A in the obtained polymer compound is represented by formula 3-1.
10. A method for producing a polymer compound according to claim 9, wherein OCN-R1-NCO：HO-R2-OH：HO-R3-OH ratio of 4:3.5:0.5 to 4:2: 2.
11. the method for producing a polymer compound according to claim 8, wherein the curing reaction includes:
reacting the polymer represented by formula 4 with moisture, wherein
A in the obtained polymer compound is represented by formula 3-2.
12. A waterproof adhesive material comprising the polymer compound according to any one of claims 1 to 3.
13. A lamp comprising a lampshade, a base and the waterproof adhesive material of claim 12, wherein the waterproof adhesive material is disposed at a joint position of the base and the lampshade.
14. A polymer compound, characterized in that a hard segment thereof includes an aromatic group, an aliphatic group or a combination thereof, and a soft segment thereof includes a group represented by formula 2-1 or formula 2-2:
in the formula 2-1, a is 0 or 1,
in formula 2-2, b is a positive integer of 3 to 6.
15. A polymer compound according to claim 14, wherein the aromatic group of the hard segment includes a benzene ring, a bis-benzene ring, pyridine, bis-pyridine, pyran or a six-membered ring heterocyclic structure, and the aliphatic group of the hard segment includes an alicyclic group, an alkene group, an alkane group, an ether group, a ketone group or an ester group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910061934.9A CN111471152A (en) | 2019-01-23 | 2019-01-23 | Polymer compound and manufacturing method thereof, waterproof adhesive material and lamp |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910061934.9A CN111471152A (en) | 2019-01-23 | 2019-01-23 | Polymer compound and manufacturing method thereof, waterproof adhesive material and lamp |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111471152A true CN111471152A (en) | 2020-07-31 |
Family
ID=71743753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910061934.9A Pending CN111471152A (en) | 2019-01-23 | 2019-01-23 | Polymer compound and manufacturing method thereof, waterproof adhesive material and lamp |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111471152A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002057215A2 (en) * | 2001-01-16 | 2002-07-25 | Theravance, Inc. | Sodium channel modulators |
| CN101475790A (en) * | 2008-01-04 | 2009-07-08 | 杨光 | Novel timber adhesive and preparation thereof |
| CN102372649A (en) * | 2010-08-19 | 2012-03-14 | Jnc株式会社 | Diamine, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display component |
| CN109206677A (en) * | 2018-09-04 | 2019-01-15 | 济南大学 | A kind of dissaving polymer modified carbon black surface and its application in rubber processing |
-
2019
- 2019-01-23 CN CN201910061934.9A patent/CN111471152A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002057215A2 (en) * | 2001-01-16 | 2002-07-25 | Theravance, Inc. | Sodium channel modulators |
| CN101475790A (en) * | 2008-01-04 | 2009-07-08 | 杨光 | Novel timber adhesive and preparation thereof |
| CN102372649A (en) * | 2010-08-19 | 2012-03-14 | Jnc株式会社 | Diamine, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display component |
| CN109206677A (en) * | 2018-09-04 | 2019-01-15 | 济南大学 | A kind of dissaving polymer modified carbon black surface and its application in rubber processing |
Non-Patent Citations (2)
| Title |
|---|
| MARKUS, RICHARD L.ETC.: "Imido glycols as stable polar liquid phases in gas chromatography", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
| MURRAY M. SPRUNG: "Mechanism of the Reaction between Phthalic Anhydride and an Aminodiol", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3206660B2 (en) | Fluorinated polyurethanes with improved mechanical properties containing rubber-like polyoxyperfluoroalkylene structural blocks and hydrogenated hard blocks | |
| JP5381977B2 (en) | Method for producing hydroxy compound, and method for producing prepolymer and polyurethane | |
| CA1271881A (en) | Silane containing isocyanate prepolymers | |
| TW201348280A (en) | Resin composition, two-liquid type adhesive for laminate, laminated film and backsheet for solar cell | |
| JP7271325B2 (en) | Polyol and crosslinkable polyurethane resin for crosslinkable polyurethane resin composition | |
| CN113980193B (en) | Optical-grade oleophilic type thermal repair resin, preparation method thereof and self-repair coating | |
| CN111471152A (en) | Polymer compound and manufacturing method thereof, waterproof adhesive material and lamp | |
| CN108285698B (en) | Self-repairable coating composition, self-repairable coating, protective film containing self-repairable coating, and application of protective film | |
| US4816544A (en) | Polyamideimide elastomer and production thereof | |
| TWI695021B (en) | Polymer, manufacturing method of the same, waterproof material and lamp | |
| JP3063342B2 (en) | Polyurethane and method for producing the same | |
| JPH07113004A (en) | Thermoplastic polyurethane elastomer and production thereof | |
| CN115029055B (en) | Weather-resistant modified polyurethane waterproof coating and preparation method thereof | |
| CN114874410B (en) | Photoinitiated self-repairing shape memory polyurethane and preparation method and application thereof | |
| JP3194394B2 (en) | Method for producing polyurethane resin | |
| CN113004501A (en) | Long-chain alkyl polyester polyol, aqueous polyurethane emulsion and preparation method thereof | |
| JP4159422B2 (en) | Process for producing aqueous polyurethane dispersions derived from polycarbonate diols | |
| JPH0120165B2 (en) | ||
| US11104759B2 (en) | Polyol for crosslinkable polyurethane resin composition, and crosslinkable polyurethane resin | |
| CN115536802B (en) | Water-based polylactic acid modified organic silicon polyurethane and preparation method and application thereof | |
| CN112851903B (en) | Preparation method of organic silicon modified waterborne polyurethane and product thereof | |
| JPH0532753A (en) | Novel polyester polyol and polyurethane resin composition using the same | |
| JPH0458491B2 (en) | ||
| US5147960A (en) | Heterofunctional diols and polyurethane elastomers manufactured therefrom | |
| CN115551899B (en) | Polyrotaxane having group containing chain formed by repeating unit of propylene oxide in cyclic molecule |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200731 |